US11214511B2 - Transparent, near infrared-shielding glass ceramic - Google Patents
Transparent, near infrared-shielding glass ceramic Download PDFInfo
- Publication number
- US11214511B2 US11214511B2 US16/559,806 US201916559806A US11214511B2 US 11214511 B2 US11214511 B2 US 11214511B2 US 201916559806 A US201916559806 A US 201916559806A US 11214511 B2 US11214511 B2 US 11214511B2
- Authority
- US
- United States
- Prior art keywords
- mol
- glass
- glasses
- phase
- nir
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
- 239000002241 glass-ceramic Substances 0.000 title description 66
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005385 borate glass Substances 0.000 claims abstract description 12
- KAMGYJQEWVDJBD-UHFFFAOYSA-N bismuth zinc borate Chemical compound B([O-])([O-])[O-].[Zn+2].[Bi+3] KAMGYJQEWVDJBD-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 Pr2O3 Inorganic materials 0.000 claims abstract description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract 3
- 230000005540 biological transmission Effects 0.000 claims description 11
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 2
- 239000011521 glass Substances 0.000 abstract description 89
- 229910016327 MxWO3 Inorganic materials 0.000 abstract description 45
- 229910052721 tungsten Inorganic materials 0.000 abstract description 27
- 239000010937 tungsten Substances 0.000 abstract description 27
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 25
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 abstract description 20
- 229910000906 Bronze Inorganic materials 0.000 abstract description 18
- 239000010974 bronze Substances 0.000 abstract description 18
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 239000006112 glass ceramic composition Substances 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 229910052700 potassium Inorganic materials 0.000 abstract description 10
- 229910052792 caesium Inorganic materials 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 abstract description 4
- 229910052693 Europium Inorganic materials 0.000 abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 abstract description 4
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 abstract description 4
- 229910052776 Thorium Inorganic materials 0.000 abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 abstract description 4
- 229910052770 Uranium Inorganic materials 0.000 abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 4
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 229910052712 strontium Inorganic materials 0.000 abstract description 4
- 229910052716 thallium Inorganic materials 0.000 abstract description 4
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 62
- 239000000203 mixture Substances 0.000 description 34
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 32
- 238000010438 heat treatment Methods 0.000 description 31
- 239000000377 silicon dioxide Substances 0.000 description 31
- 229910052681 coesite Inorganic materials 0.000 description 29
- 229910052906 cristobalite Inorganic materials 0.000 description 29
- 229910052682 stishovite Inorganic materials 0.000 description 29
- 229910052905 tridymite Inorganic materials 0.000 description 29
- 239000000243 solution Substances 0.000 description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000000155 melt Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 11
- 239000005373 porous glass Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 238000000137 annealing Methods 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 9
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 9
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000005354 aluminosilicate glass Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000012080 ambient air Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910003069 TeO2 Inorganic materials 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005365 phosphate glass Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ARTGXHJAOOHUMW-UHFFFAOYSA-N boric acid hydrate Chemical compound O.OB(O)O ARTGXHJAOOHUMW-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940006165 cesium cation Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000007783 splat quenching Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006058 strengthened glass Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical class O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/04—Compositions for glass with special properties for photosensitive glass
- C03C4/06—Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass
- C03C4/065—Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass for silver-halide free photochromic glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/18—Compositions for glass with special properties for ion-sensitive glass
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
Definitions
- the disclosure relates to glass ceramic materials. More particularly, the disclosure relates to optically transparent glass ceramic materials. Even more particularly, the disclosure relates to optically transparent glass ceramic materials having a crystalline tungsten bronze phase.
- NIR-shielding glasses are being developed to block and/or eliminate wavelengths ranging from 700-2500 nm for applications ranging from optical filters, lenses, and glazing for medical, defense, aerospace, and consumer applications.
- Low emittance (low-E) coatings have been developed to minimize the amount of ultraviolet and infrared light that can pass through glass without compromising the amount of visible light that is transmitted.
- Low-E coatings are typically either sputtered or pyrolytic coatings.
- low-E plastic laminates may be retrofitted to a glass substrate.
- tungsten bronzes thin films, coatings, and composite materials containing nano- or micron-sized particles of non-stoichiometric tungsten suboxides or doped non-stoichiometric tungsten trioxides (referred to as tungsten bronzes) have been used to provide near infrared shielding with high transparency in the visible spectrum.
- tungsten bronze films often require expensive vacuum deposition chambers, have limited mechanical robustness, and are susceptible to oxygen, moisture, and UV light, all of which cause the NIR shielding performance of these materials to decrease and to discolor and degrade transparency in the visible light range.
- the present disclosure provides optically transparent glass ceramic materials which, in some embodiments, comprise a glass phase containing at least about 80% silica by weight and a crystalline tungsten bronze phase having the formula M x WO 3 , where M includes, but is not limited to, at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 ⁇ x ⁇ 1.
- the crystalline tungsten bronze phase comprises nanoparticles.
- the glass ceramic in some embodiments, has a low coefficient of thermal expansion (CTE), strong attenuation or blocking of ultraviolet (UV) radiation at wavelengths of less than about 360 nm and near infrared (NIR) radiation at wavelengths ranging from about 700 nm to about 3000 nm.
- CTE coefficient of thermal expansion
- UV radiation ultraviolet
- NIR near infrared
- Aluminosilicate and zinc-bismuth-borate glasses comprising at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 are also provided.
- one aspect of the disclosure is to provide a glass ceramic comprising a silicate glass phase and from about 1 mol % to about 10 mol % of a crystalline M x WO 3 phase comprising nanoparticles, where M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 ⁇ x ⁇ 1.
- a second aspect of the disclosure is to provide a glass ceramic comprising a silicate glass phase and from about 1 mol % to about 10 mol % of a crystalline M x WO 3 phase comprising nanoparticles, where M is at least one alkali metal, and 0 ⁇ x ⁇ 1.
- an aluminosilicate glass comprising SiO 2 , Al 2 O 3 , and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , where Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 30 mol %.
- the aluminosilicate glass in some embodiments, comprises from about 8 mol % to about 45 mol % Al 2 O 3 , from about 40 mol % to about 72 mol % SiO 2 and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , wherein Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 30 mol %.
- the aluminosilicate glass further comprises at least one alkaline earth oxide and B 2 O 3 .
- the glasses in some embodiments, have less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm.
- a zinc-bismuth-borate glass comprising ZnO, Bi 2 O 3 , B 2 O 3 , and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , where Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 12 mol %.
- the Zn—Bi-borate glasses further comprise at least one of Na 2 O and TeO 2 . These glasses, in some embodiments, have less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm.
- a phosphate glass comprising at least one rare earth oxide Ln 2 O 3 and having a molar ratio 25Ln 2 O 3 :75P 2 O 5 , where Ln 2 O 3 comprises at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 is provided.
- the phosphate glass comprises: from about 6 mol % to about 25% Ln 2 O 3 ; from about 5 mol % to about 27% Al 2 O 3 ; and from about 67 mol % to about 74 mol % P 2 O 5 .
- FIG. 1 is a plot of absorbance vs. wavelength of splat-quenched, annealed, and heat-treated glass ceramic samples
- FIG. 2 is a plot of spectra of splat-quenched (A), annealed (B), and heat-treated (C) glass ceramic compositions;
- FIG. 3 is a plot of differential scanning calorimetry cooling curves measured for glass ceramic samples
- FIG. 4 is a plot of spectra of glass ceramics containing different alkali tungsten bronzes
- FIG. 5 is an x-ray powder diffraction profile of a splat-quenched glass ceramic
- FIG. 6 is an x-ray powder diffraction profile of a heat-treated glass ceramic
- FIG. 7 is a flow chart for a method of infiltrating a glass to form a glass ceramic
- FIG. 8 is a plot of a dispersion curve for glass E listed in Table E;
- FIG. 9 is a plot of transmission for glass E listed in Table E.
- FIG. 10 is a plot of transmission for glasses J, K, and L listed in Table F.
- glass article and “glass articles” are used in their broadest sense to include any object made wholly or partly of glass and/or glass ceramics, and includes laminates of the glasses and glass ceramics described herein with conventional glasses. Unless otherwise specified, all compositions are expressed in terms of mole percent (mol %). Coefficients of thermal expansion (CTE) are expressed in terms of 10 ⁇ 7 /° C. and represent a value measured over a temperature range from about 20° C. to about 300° C., unless otherwise specified.
- CTE coefficients of thermal expansion
- nanoparticle and “nanoparticles” refer to particles between about 1 and about 1,000 nanometers (nm) in size.
- platelet and “platelets” refer to flat or planar crystals.
- nanorod and “nanorods” refer to elongated crystals having a length of up to about 1,000 nm and an aspect ratio (length/width) of at least 3 and in some embodiments, in a range from about 3 to about 5.
- transmission and “transmittance” refer to external transmission or transmittance, which takes absorption, scattering and reflection into consideration. Fresnel reflection is not subtracted out of the transmission and transmittance values reported herein.
- a glass that is “free of MgO” is one in which MgO is not actively added or batched into the glass, but may be present in very small amounts (e.g., less than 400 parts per million (ppm), or less than 300 ppm) as a contaminant.
- Compressive stress and depth of layer are measured using those means known in the art.
- Such means include, but are not limited to, measurement of surface stress (FSM) using commercially available instruments such as the FSM-6000, manufactured by Orihara Co., Ltd. (Tokyo, Japan).
- FSM surface stress
- FSM-6000 manufactured by Orihara Co., Ltd. (Tokyo, Japan).
- SOC stress optical coefficient
- ASTM standard C770-98 (2013) entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.
- the modification of Procedure C includes using a glass disc as the specimen having a thickness of 5 to 10 mm and a diameter of 12.7 mm.
- the disc is isotropic and homogeneous, and is core-drilled with both faces polished and parallel.
- the modification also includes calculating the maximum force, Fmax to be applied to the disc.
- the force should be sufficient to produce at least 20 MPa compression stress.
- ⁇ (MPa) 8 F /( ⁇ D ⁇ h )
- F is the force, expressed in Newtons
- D is the diameter of the disc, expressed in millimeters (mm)
- h is the thickness of the light path, also expressed in millimeters.
- depth of layer refers to the depth of the compressive layer as determined by surface stress measurements (FSM) measurements using commercially available instruments such as, but not limited to, the FSM-6000 stress meter.
- the depth of compression DOC refers to the depth at which the stress is effectively zero inside the glass and can be determined from the stress profile obtained using the refractive near field (RNF) and polarimetric methods that are known in the art. This DOC is typically less than the FSM_DOL measured by the FSM instrument for a single ion exchange process.
- the FSM technique may suffer from contrast issues that affect the observed DOL value.
- the FSM software analysis is incapable of determining the compressive stress profile (i.e., the variation of compressive stress as a function of depth within the glass).
- the FSM technique is incapable of determining the depth of layer resulting from the ion exchange of certain elements in the glass such as, for example, the ion exchange of sodium for lithium.
- the DOL as determined by the FSM is a relatively good approximation for the depth of the compressive layer of depth compression (DOC) when the DOL is a small fraction r of the thickness t and the index profile has a depth distribution that is reasonably well approximated with a simple linear truncated profile.
- DOC compressive layer of depth compression
- the compressive stress, stress profile, and depth of layer may be determined using scattered linear polariscope (SCALP) techniques that are known in the art.
- SCALP scattered linear polariscope
- the SCALP technique enables non-destructive measurement of surface stress and depth of layer.
- optically transparent glass ceramic materials which, in some embodiments, comprise a glass phase containing at least about 90% silica by weight and a crystalline tungsten bronze phase.
- These glass ceramics comprise a silicate glass phase and from about 0.1 mol % to about 10 mol %, or from about 1 mol % to about 4 mol %, or from about 0.5 mol % to about 5 mol % of a crystalline tungsten bronze phase comprising crystalline M x WO 3 nanoparticles.
- the crystalline M x WO 3 nanoparticles are encapsulated within and dispersed within and, in some embodiments, throughout the residual glass phase.
- the M x WO 3 crystalline nanoparticles are disposed at or near the surface of the glass ceramic.
- the M x WO 3 crystalline nanoparticles are platelet-shaped and have an average diameter, determined by those means known in the art (e.g., SEM and/or TEM microscopy, x-ray diffraction, light scattering, centrifugal methods, etc.) ranging from about 10 nm to 1000 nm, or from about 10 nm to about 5 ⁇ m, and/or M x WO 3 nanorods having a high aspect ratio and an average length, determined by those means known in the art, ranging from 10 nm to 1000 nm, and an average width, determined by those means known in the art, ranging from about 2 to about 75 nm.
- tungsten bronze glass ceramics that exhibit high visible transparency and strong UV and NIR absorption contain high aspect ratio (length/width) M x WO 3 rods having an average length ranging from about 10 nm to about 200 nm and an average width ranging from about 2 nm to 30 nm.
- the crystalline tungsten bronze phase has the formula M x WO 3 , where M is at least one of H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Cu, Ag, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0 ⁇ x ⁇ 1.
- These glass ceramics have a low coefficient of thermal expansion (CTE), strong attenuation or blocking of ultraviolet (UV) radiation at wavelengths of less than about 250 nm and near infrared (NIR) radiation at wavelengths ranging from about 700 nm to about 2500 nm.
- CTE coefficient of thermal expansion
- UV radiation ultraviolet
- NIR radiation near infrared
- the glass ceramics described herein are optically transparent in the visible (i.e., wavelengths from about 400 nm to about 700 nm) region of the spectrum. That is, the glass ceramic has a transmittance of greater than about 1% over a 1 mm path (expressed herein as “%/mm”) over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
- the glass ceramic has a transmittance of at least greater than about 10%/mm, in other embodiments, greater than about 50%/mm, in other embodiments, greater than about 75%/mm, in other embodiments, greater than about 80%/mm, and in still other embodiments, greater than about 90%/mm over at least one 50 nm-wide wavelength band of light in the visible region of the spectrum.
- these glass ceramics absorb light in the ultraviolet (UV) region (wavelengths of less than about 370 nm) and near infrared (NIR) region (from greater than about 700 nm to about 1700 nm) of the spectrum without use of coatings or films, which are mechanically fragile and sensitive to UV light and moisture.
- UV ultraviolet
- NIR near infrared
- the glass ceramic has a transmittance of less than 5%/mm and, in other embodiments, less than 1%/mm for light having a wavelength of about 370 nm or less. In some embodiments, the glass ceramic has an absorption of at least 90%/mm, in other embodiments, at least than 95%/mm, and in other embodiments, at least than 99%/mm for light having a wavelength of about 370 nm or less. In some embodiments, the glass ceramic has a transmittance of less than 10%/mm and, in other embodiments, less than 5%/mm over at least one 50 nm-wide wavelength band of light for light in the NIR region (i.e., from about 700 nm to about 2500 nm) of the spectrum.
- the glass ceramic has an absorption of at least 90%/mm and, in other embodiments, at least 95%/mm over at least one 50 nm-wide wavelength band of light for light in the NIR region (i.e., from about 700 nm to about 2500 nm) of the spectrum.
- the glass ceramics described herein are capable of withstanding temperatures of at least about 300° C., or, in some embodiments, at least about 200° C., without impairing their optical or mechanical properties.
- the transmittance of the glass ceramic between about 500 nm and about 2500 nm changes by less than 10%/mm when the glass ceramic is heated at temperatures in a range from about 200° C. to about 300° C. for periods of at least one hour.
- These glass ceramics are, in some embodiments, unreactive and otherwise impervious to oxygen, hydrogen, and moisture.
- the glass ceramics described herein have a coefficient of thermal expansion (CTE) at temperatures ranging from about 0° C. to about 300° C. of about 75 ⁇ 10 ⁇ 7 ° C. ⁇ 1 . In some embodiments, the glass ceramics have a coefficient of thermal expansion (CTE) at temperatures ranging from about 0° C. to about 300° C. from about 33.5 ⁇ 10 ⁇ 7 ° C. ⁇ 1 to about 66.3 ⁇ 10 7 ° C. ⁇ 1 (e.g., samples 2, 11, 12, 13, and 54 in Table 1).
- CTE coefficient of thermal expansion
- the glass ceramics described herein are bleachable—i.e., the crystalline M x WO 3 may be “erased” by thermally treating the glasses/glass ceramics for a short period above their respective softening points. Such thermal treatment may be performed using those energy sources known in the art, such as, but not limited to, resistance furnaces, lasers, microwaves, or the like.
- Composition 37 (Table 1), for example, may be bleached by holding the material at a temperature between about 685° C. and about 740° C. for approximately 5 minutes.
- the M x WO 3 bronze phase may then be re-formed or re-crystallized on the surface of the material by exposure to a UV-pulsed laser; i.e., the tungsten bronze phase will be re-formed in those areas exposed to the laser.
- the glass ceramics described herein may be used for low-emittance glazing in architectural, automotive, medical, aerospace, or other applications, including thermal face shields, medical eyewear, optical filters, and the like.
- the glass ceramic forms a portion of a consumer electronic product, such as a cellular phone or smart phone, laptop computer, tablet, or the like.
- consumer electronic products typically comprise a housing having front, back, and side surfaces, and includes electrical components, which are at least partially internal to the housing.
- the electrical components include at least a power source, a controller, a memory, and a display.
- the glass ceramic described herein comprises at least a portion of a protective element, such as, but not limited to, the housing and/or display.
- the glass phase is a borosilicate glass and the glass ceramic comprises SiO 2 , Al 2 O 3 , B 2 O 3 , WO 3 , and at least one alkali metal oxide R 2 O, where R 2 O is at least one of Na 2 O, K 2 O, Cs 2 O, and/or Rb 2 O, and the crystalline tungsten bronze phase is an tungsten bronze solid solution containing, comprising, or consisting essentially of MWO 3 , where M is at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O.
- the glass ceramic comprises: from about 56 mol % to about 78 mol % SiO 2 (56 mol % ⁇ SiO 2 ⁇ 78 mol %) or from about 60 mol % to about 78 mol % SiO 2 (60 mol % ⁇ SiO 2 ⁇ 78 mol %); from about 8 mol % to about 27 mol % B 2 O 3 (8 mol % ⁇ B 2 O 3 ⁇ 27 mol %); from about 0.5 mol % to about 14 mol % Al 2 O 3 (0.5 mol % ⁇ Al 2 O 3 ⁇ 14 mol %); from greater than 0 mol % to about 10 mol % of at least one of Na 2 O, K 2 O, Cs 2 O, and Rb 2 O (0 mol % ⁇ Na 2 O+K 2 O+Cs 2 O+Rb 2 O ⁇ 9 mol %); from about 1 mol % to about 10 mol % WO 3 (1 mol % ⁇ WO 3
- the glass ceramic may comprise from 0 mol % to about 9 mol % Li 2 O; in some embodiments, from 0 mol % to about 9 mol % Na 2 O (0 mol % ⁇ Na 2 O ⁇ 9 mol %); in some embodiments, from 0 mol % to about 9 mol % K 2 O (0 mol % ⁇ K 2 O ⁇ 9 mol %) or from 0 mol % to about 3 mol % K 2 O (0 mol % ⁇ K 2 O ⁇ 3 mol %); in some embodiments, from 0 mol % to about 10 mol % Cs 2 O (0 mol % ⁇ Cs 2 O ⁇ 10 mol %) or from greater than 0 mol % to about 7 mol % Cs 2 O (0 mol % ⁇ Cs 2 O ⁇ 7 mol %); and/or, in some embodiments, from 0 mol % to about 9 mol % Rb 2 O (0 mol % ⁇ Rb 2 O ⁇ 9
- the glass ceramic may further comprise at least one of: up to about 0.5 mol % MgO (0 mol % ⁇ MgO ⁇ 0.5 mol %); up to about 2 mol % P 2 O 5 (0 mol % ⁇ P 2 O 5 ⁇ 2 mol %); and up to about 1 mol % (0 mol % ⁇ ZnO ⁇ 1 mol %).
- the rate of formation of M x WO 3 upon cooling or heat treatment may be increased by the addition of at least one of MgO (e.g., samples 55, 56, and 57 in Table 1), P 2 O 5 . (e.g., sample 58 in Table 1), and ZnO up (e.g., sample 59 in Table 1).
- Non-limiting compositions of glass ceramics that are transparent in the visible light range and UV and NIR-absorbing are listed in Table 1. Compositions that do not absorb either UV or NIR radiation are listed in Table 2.
- peraluminous melts may be divided into three sub-categories.
- the term “peraluminous melts” refer to melts in which the molar proportion or content of alumina that is greater than that of R 2 O, where R 2 O is at least one of Li 2 O, Na 2 O, K 2 O, and Cs 2 O; i.e. Al 2 O 3 (mol %)>R 2 O(mol %).
- the first sub-category is one in which peraluminous melts, when quenched rapidly from the molten state and after annealing, are transparent in the visible wavelength range and NIR regime (e.g., samples 12, 15-17, 20, 23, 25, 33, 35-42, 44, 46, 47, and 48 in Table 1). These materials require a subsequent heat treatment at or slightly above the anneal temperature but below the softening point in order to develop the NIR-absorbing nanocrystalline M x WO 3 phase.
- FIG. 1 is a plot of absorbance vs. wavelength for splat-quenched, annealed, and heat-treated samples of composition 13.
- the term “splat-quenching” refers to the process of pouring a small amount or “glob” of molten glass onto an iron plate that is at room temperature and immediately pressing the glob with an iron plunger (also at room temperature) so as to rapidly cool the glass and press the glob into a thin (3-6 mm) disc of glass. While the splat-quenched (A in FIG.
- composition/sample 13 show no absorption in the visible or NIR regimes, those samples that have been heat treated (C, D, E) exhibit absorbance in the NIR regime that increases with increasing heat treatment time, as well as some visible light attenuation at wavelengths in the 600-700 nm range, resulting in a material having a blue hue.
- the second category of peraluminous melts remains transparent in the visible and NIR regimes if rapidly quenched, but exhibits NIR absorption post annealing (see samples 12, 14, 19, 21, 22, 24, and 26-32 in Table 1).
- FIG. 2 which shows spectra of splat-quenched (A), annealed (B), and heat-treated (C) samples of glass ceramic composition 11, the NIR absorbance of the splat-quenched or annealed glass ceramic may be enhanced by further heat treatment.
- the third category of peraluminous melts exhibits NIR absorption even upon rapid quenching (see samples 1 and 7 in Table 1).
- the NIR absorption of these materials may be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.
- UV- and NIR-absorbing melts were transparent in the visible and NIR when rapidly quenched but were NIR-absorbing after annealing. As with the melts previously described hereinabove, NIR absorption may be further enhanced by subsequent heat treatment at or above the annealing point, but below the softening point.
- the rate of formation of the crystalline M x WO 3 phase may also be tuned by adjusting at least one of heat treatment time and temperature; the (R 2 O(mol %)+Al 2 O 3 (mol %))/WO 3 (mol %) ratio; the R 2 O(mol %)/WO 3 (mol %) ratio; the Al 2 O 3 (mol %)/WO 3 (mol %) ratio; and selection of alkali (or alkalis) to be batched.
- more of the crystalline M x WO 3 phase precipitates with longer heat treatment times, resulting in a material having stronger NIR absorption.
- excessive heat treatment times may cause the crystalline M x WO 3 phase to coarsen.
- coarsening may be accompanied by formation of a secondary or tertiary crystalline phase such as borastalite or aluminum borate.
- the formation of these secondary phases may produce a material that scatters visible wavelengths of light and thus appears hazy or opalescent.
- the rate of M x WO 3 formation in most instances increases as the heat treatment temperature increases and approaches the softening point of the glass.
- the rate of M x WO 3 formation decreases.
- the NIR-absorbing crystalline M x WO 3 phase ceases to precipitate from the melt.
- the ratio R 2 O(mol %)/WO 3 (mol %) is greater than or equal to 0 and less than or equal to about 4 (0 ⁇ R 2 O(mol %)/WO 3 (mol %) ⁇ 4), and the ratio Al 2 O 3 (mol %)/WO 3 (mol %) is in a range from about 0.66 and about 6 (0.66 ⁇ Al 2 O 3 (mol %)/WO 3 (mol %) ⁇ 6).
- R 2 O(mol %)/WO 3 (mol %) is greater than 4 (R 2 O(mol %)/WO 3 (mol %)>4), the glasses may precipitate a dense immiscible second phase and separate, resulting in an inhomogeneous melt.
- the glasses cease to precipitate the crystalline M x WO 3 NIR-absorbing phase.
- the R 2 O(mol %)/WO 3 (mol %) ratio is in a range from about 0 to about 3.5 (0 ⁇ R 2 O/WO 3 ⁇ 3.5) (e.g., sample 26 in Table 1).
- R 2 O/WO 3 is in a range from about 1.25 and about 3.5 (1.25 ⁇ R 2 O(mol %)/WO 3 (mol %) ⁇ 3.5) (e.g., sample 53 in Table 1), as samples in this compositional range rapidly precipitate the UV and NIR absorbing M x WO 3 crystalline phase, exhibit high visible transparency with strong NIR absorption, and are bleachable (i.e., the M x WO 3 crystalline phase can be “erased”).
- the ratio Al 2 O 3 (mol %)/WO 3 (mol %) is, in certain embodiments, is in a range from about 0.66 and about 4.5 (0.66 ⁇ Al 2 O 3 (mol %)/WO 3 (mol %) ⁇ 4.5) (e.g., sample 40 in Table 1), and, most preferably, Al 2 O 3 (mol %)/WO 3 (mol %) is is in a range from about 2 to about 3 (1 ⁇ Al 2 O 3 (mol %)/WO 3 (mol %) ⁇ 3) (e.g., sample 61 in Table 1). Above this range, the NIR absorbing nanocrystalline M x WO 3 bronze forms slowly.
- DSC differential scanning calorimetry
- the peak or maximum transmission wavelength in the visible range and NIR absorption edge of the glass ceramic may be tuned through composition, heat treatment time and temperature, and alkali metal oxide selection.
- Spectra of glass ceramics containing different alkali tungsten bronzes and otherwise having identical compositions are shown in FIG. 4 .
- the potassium and cesium analogs (samples 16 and 13, respectively) and have shorter peak visible transmittance wavelengths (440-450 nm) than the sodium and lithium analogs (samples 15 and 14, respectively), which have peak visible transmittance wavelengths of 460 nm and 510 nm, respectively.
- the glass ceramics described herein have a lower boron concentration—i.e., from about 9.8 mol % to about 11.4 mol % B 2 O 3 (9.8 mol % ⁇ B 2 O 3 ⁇ 11.4 mol %).
- the NIR-absorbing crystalline M x WO 3 phase is precipitated over a narrow and low temperature range, as shown in Table B. These compositions may be heated above their respective softening points and sagged, slumped, or formed, without growing the crystalline M x WO 3 phase.
- composition 44 can be bleached by holding the material at a temperature between about 685° C. and about 740° C. for approximately 5 minutes.
- these glasses and glass ceramics may be patterned with UV lasers.
- the M x WO 3 phase may be precipitated in rapidly quenched compositions (e.g., sample 14 in Table 1), for example, by exposing the material exposed to a 10 watt 355 nm pulsed laser.
- Table C lists physical properties, including strain, anneal and softening points, coefficients of thermal expansion (CTE), density, refractive indices, Poisson's ratio, shear modulus, Young's modulus, liquidus (maximum crystallization) temperature, and the stress optical coefficient (SOC) measured for selected sample compositions listed in Table 1.
- XRD x-ray powder diffraction
- FIGS. 5 and 6 are representative XRD profiles obtained for splat-quenched and heat-treated materials, both having composition 14 in Table 1, respectively. These XRD profiles demonstrate that as-quenched materials ( FIG. 5 ) are amorphous and do not contain a crystalline M x WO 3 phase prior to heat treatment, and heat-treated glass materials contain a crystalline M x WO 3 second phase.
- the glass ceramic may be ion exchangeable.
- Ion exchange is commonly used to chemically strengthen glasses.
- alkali cations within a source of such cations e.g., a molten salt, or “ion exchange,” bath
- CS compressive stress
- DOL depth of layer
- DOC depth of compression DOC
- the glass ceramic is ion exchanged and has a compressive layer extending from at least one surface to a depth (as indicated by DOC and/or DOL) of at least about 10 ⁇ m within the glass ceramic.
- the compressive layer has a compressive stress CS of at least about 100 MPa and less than about 1500 MPa at the surface.
- compositions 51 and 54 were ion exchanged.
- the samples were first heat-treated at 550° C. for 15 hours, then cooled at 1° C./min to 475° C., and further cooled to room temperature at the rate of cooling of the furnace when power is shut off (furnace rate).
- the cerammed samples were then ion exchanged at 390° C. for 3 hours in a molten bath of KNO 3 resulting in surface compressive stresses of 360 MPa and 380 MPa and depths of layers of 31 and 34 microns for glass-ceramic compositions 51 and 54, respectively.
- the glass ceramics described herein may be made using a melt quench process. Appropriate ratios of the constituents may be mixed and blended by turbulent mixing or ball milling. The batched material is then melted at temperatures ranging from about 1550° C. to about 1650° C. and held at temperature for times ranging from about 6 to about 12 hours, after which time it may be cast or formed and then annealed. Depending on the composition of the material, additional heat treatments at or slightly above the annealing point, but below the softening point, to develop the crystalline M x WO 3 second phase and provide UV- and NIR-absorbing properties.
- the glass ceramic is formed by infiltrating a nano-porous glass such as, but not limited to, VYCOR®, a high-silica glass manufactured by Corning Incorporated.
- a nano-porous glass such as, but not limited to, VYCOR®, a high-silica glass manufactured by Corning Incorporated.
- Such nano-porous glasses may be 20 to 30% porous with a 4.5-16.5 nm average pore diameter, with a narrow pore size distribution (with about 96% of the pores in the glass being +0.6 nm from the average diameter).
- the average pore diameter may be increased to about 16.5 nm by adjusting the heat treatment schedule required to phase separate the glass and by modifying etching conditions.
- FIG. 7 A flow chart for the method of infiltrating a glass and forming the glass ceramic is shown in FIG. 7 .
- a first solution containing tungsten, a second solution containing the metal cation M, and a third solution of boric acid are prepared or provided to deliver these components to a nano-porous glass substrate.
- the tungsten solution is prepared by dissolving ammonium metatungstate (AMT) in deionized water to produce a desired concentration of tungsten ions.
- AMT ammonium metatungstate
- organic precursors such as tungsten carbonyl, tungsten hexachloride, or the like may be used to deliver the tungsten into the pores of the nano-porous glass substrate.
- a number of aqueous precursors, including nitrates, sulfates, carbonates, chlorides, or the like may also be used to provide the metal M cation in the M x WO 3 bronze.
- a first aqueous solution of 0.068 M AMT and a second aqueous solution 0.272 M of cesium nitrate are prepared or provided such that the cesium cation concentration is 1 ⁇ 3 of the tungsten cation concentration.
- the third solution is a super-saturated boric acid solution which, in some embodiments, may be prepared by adding boric acid hydrate to deionized water, and heating the mixture to boiling while stirring.
- the nano-porous glass may be cleaned prior to forming the glass ceramic.
- Samples e.g., 1 mm sheets
- Samples may first be slowly heated in ambient air to a temperature of about 550° C. to remove moisture and organic contaminants, and subsequently kept stored at about 150° C. until ready for use.
- the nano-porous glass is first infiltrated with the tungsten solution (step 120 ) by immersing the glass in the first, tungsten-containing solution at room temperature (about 25° C.). In one non-limiting example, the nano-porous glass is immersed in the first solution for about one hour. The glass sample may then be removed from the first solution, soaked for about one minute in deionized water, and dried in ambient air for times ranging from about 24 to about 72 hours.
- the infiltrated nano-porous glass sample is heated in flowing oxygen to decompose the ammonium tungsten metatungstate and form WO 3 (step 130 ).
- the glass is first heated to about 225° C. at a rate of about 1° C./minute, then heated from about 225° C. to about 450° C. at a rate of 2.5° C./minute followed by a four hour hold at 450° C., and then cooled from about 450° C. to room temperature at a rate in a range from about 5° C. to about 7° C. per minute.
- Step 130 may, in some embodiments, include pre-heating the glass at about 80° C. for up to about 24 hours prior to the above heat treatment.
- the glass is immersed in the second solution (step 140 ) at room temperature (about 25° C.) to infiltrate the glass with the M cation solution.
- Step 140 may, in some embodiments, be preceded by pre-heating the glass at about 80° C. for up to about 24 hours prior to immersion.
- the nano-porous glass is immersed in the second solution for about one hour.
- the glass sample may then be removed from the second solution, soaked for about one minute in deionized water, and dried in ambient air for times ranging from about 24 to about 72 hours.
- Heating step 150 includes first heating the glass from about 5° C. to about 200° C. at a rate (ramp rate) of about 1° C./minute in a nitrogen atmosphere, followed by heating from about 200° C. to about 575° C. at a rate of about 3° C./minute under an atmosphere of 3% hydrogen and 97% nitrogen and a one hour hold at 575° C., and then rapidly cooling the glass to about 300° C. by opening the furnace in which the heating step takes place.
- the sample is then left to stand in ambient air for an unspecified time.
- the glass sample is immersed in the third solution, which is a supersaturated boric acid solution (step 160 ).
- the third solution is maintained at boiling and gently stirred during step 160 .
- the glass sample is immersed in the boiling solution for about 30 minutes.
- the sample in some embodiments, is washed with deionized water and left to stand in ambient air for about 24 hours.
- the glass is then heated under a nitrogen atmosphere to form and consolidate the glass ceramic (step 170 ).
- the glass is first heated from room temperature to about 225° C. at a ramp rate of about 1° C./minute in step 170 , followed by heating from about 225° C. to about 800° C. at a rate of about 5° C./minute.
- the glass is held at 800° C. for about one hour and then cooled from about 800° C. to room temperature at a rate of about 10° C./minute.
- glasses doped with rare earth oxides and having high absorbance in the NIR region of the spectrum are provided.
- these REO-doped glasses contribute to high refractive index of the glass in the infrared (IR).
- the rare earth oxide dopants which include Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , comprise up to about 30 mol % of the glass.
- the REO-doped glasses are aluminosilicate glasses comprising Al 2 O 3 and SiO 2 and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , where Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 30 mol %, in some embodiments, Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 28 mol % and, in other embodiments, Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 25 mol %. In some embodiments, these REO-doped glasses may comprise up to about 30 mol % Pr 2 O 3 or up to about 25 mol % Pr 2 O 3 .
- these REO-doped glasses may comprise up to 28 mol % Sm 2 O 3 or up to 26 mol % Sm 2 O 3 .
- the REO-doped aluminosilicate glasses may comprise from about 40 mol % to about 72 mol % SiO 2 (40 mol % ⁇ SiO 2 ⁇ 72 mol %) or from about 50 mol % to about 72 mol % SiO 2 (50 mol % ⁇ SiO 2 ⁇ 72 mol %) and from about 8 mol % to about 45 mol % Al 2 O 3 (8 mol % ⁇ Al 2 O 3 ⁇ 45 mol %), or from about 8 mol % to about 20 mol % Al 2 O 3 (8 mol % ⁇ Al 2 O 3 ⁇ 20 mol %) or from about 8 mol % to about 18 mol % Al 2 O 3 (8 mol % ⁇ Al 2 O 3 ⁇ 18 mol %).
- the glasses further comprise at least one alkaline earth oxide and/or B 2 O 3 , where 0 mol % ⁇ MgO+CaO+BaO ⁇ 24 mol % and 0 mol % ⁇ B 2 O 3 ⁇ 6 mol %.
- the glasses in some embodiments, have less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm.
- Non-limiting examples of compositions of aluminosilicate glasses are listed in Table E. Refractive indices (RI) measured for these glasses are also listed in Table E. Glasses A, B and C, which contain no alkaline earth modifiers, were found to be too viscous to pour, even at 1650° C.
- Glasses E and F which contain appreciable amounts (>21 mol %) of alkaline earth modifiers, as well as B 2 O 3 are pourable at 1650° C. Dispersion and percent transmittance for Glass E for both the visible and NIR regions of the spectrum are plotted in FIGS. 8 and 9 , respectively. Glass E exhibits both a high refractive index in the infrared (IR) region and high absorbance at 1550 nm. UV-VIS-IR spectra of these compositions containing 3-5 mol %% Pr 2 O 3 are plotted in FIG. 10 , and show the high absorbance of these glasses at 1550 nm.
- IR infrared
- the REO-doped glasses are zinc-bismuth-borate glasses comprising ZnO, Bi 2 O 3 , B 2 O 3 , and at least one of Sm 2 O 3 , Pr 2 O 3 , and Er 2 O 3 , where Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 10 mol % or, in other embodiments, Sm 2 O 3 +Pr 2 O 3 +Er 2 O 3 ⁇ 5 mol %.
- these REO-doped glasses may comprise up to about 10 mol % Pr 2 O 3 . In other embodiments, these REO-doped glasses may comprise up to 10 mol % Sm 2 O 3 .
- the REO-doped Zn—Bi-borate glasses may comprise from about 20 mol % to about 30 mol % ZnO (20 mol % ⁇ ZnO ⁇ 30 mol %), from about 4 mol % to about 20 mol % Bi 2 O 3 (4 mol % ⁇ Bi 2 O 3 ⁇ 20 mol %), and from about 40 mol % to about 50 mol % B 2 O 3 (40 mol % ⁇ B 2 O 3 ⁇ 50 mol %).
- the REO-doped Zn-Bi-borate glasses further comprise at least one of Na 2 O and TeO 2 , where 0 mol % ⁇ TeO 2 ⁇ 6 mol % and 0 mol % ⁇ Na 2 O ⁇ 15 mol %.
- the glasses in some embodiments, have less than about 30% transmission at a wavelength between about 1400 nm and about 1600 nm.
- Non-limiting examples of compositions of Zn—Bi-borate glasses are listed in Table F. Refractive indices (RI) measured for these glasses are also listed in Table F.
- the REO-doped glasses described herein are phosphate or aluminophosphate glasses.
- such glasses comprise from about 6 mol % to about 22.5% Sm 2 O 3 (6 mol % ⁇ Sm 2 O 3 ⁇ 22.5 mol %), from about 5 mol % to about 27% Al 2 O 3 (5 mol % ⁇ Al 2 O 3 ⁇ 27 mol %), and from about 67 mol % to about 74 mol % P 2 O 5 (67 mol % ⁇ P 2 O 5 ⁇ 67 mol %).
- Non-limiting examples of compositions of samarium-doped aluminophosphate glasses are listed in Table G.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Glass Compositions (AREA)
- Surface Treatment Of Glass (AREA)
- Details Of Aerials (AREA)
Abstract
Description
Fmax=7.854·D·h
where: Fmax is maximum force, expressed in Newtons; D is the diameter of the disc, expressed in millimeters (mm); and h is the thickness of the light path, also expressed in mm. For each force applied, the stress is computed using the equation:
σ (MPa)=8F/(π·D·h)
where: F is the force, expressed in Newtons; D is the diameter of the disc, expressed in millimeters (mm); and h is the thickness of the light path, also expressed in millimeters.
TABLE 1 |
Compositions of glass ceramics that are optically transparent in the visible light |
range and absorbing in the UV and NIR light ranges. |
Mol % | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
SiO2 | 76.9 | 75.9 | 72.9 | 69.9 | 65.9 | 77.6 | 76.9 | 61.7 | 61.7 | 65.9 |
B2O3 | 17 | 17 | 20 | 23 | 27 | 20 | 17 | 20 | 20 | 20 |
Al2O3 | 2 | 2 | 2 | 2 | 2 | 0.66 | 1.32 | 6.6 | 6.6 | 5 |
Li2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Na2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 1 | 2 | 2 | 2 | 2 | 0.66 | 0.66 | 1.32 | 6.6 | 5 |
WO3 | 3 | 3 | 3 | 3 | 3 | 1 | 1 | 1 | 5 | 4 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 |
SiO2 | 64.9 | 63.9 | 63.9 | 63.9 | 63.9 | 63.9 | 62.9 | 61.9 | 64.9 | 62.9 |
B2O3 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
Al2O3 | 5 | 7 | 9 | 9 | 9 | 9 | 10 | 11 | 9 | 9 |
Li2O | 0 | 0 | 0 | 3 | 0 | 0 | 0 | 0 | 0 | 0 |
Na2O | 0 | 0 | 0 | 0 | 3 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 0 | 0 | 3 | 0 | 0 | 0 | 0 |
Cs2O | 5 | 5 | 3 | 0 | 0 | 0 | 3 | 3 | 2 | 4 |
WO3 | 5 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
SiO2 | 63.9 | 61.9 | 63.9 | 63.9 | 63.9 | 64 | 64.4 | 64.9 | 65.4 | 64.9 |
B2O3 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
Al2O3 | 10 | 12 | 9 | 9 | 9 | 9 | 9 | 9 | 9 | 9 |
Li2O | 0 | 0 | 0 | 1.5 | 1.5 | 3 | 3 | 3 | 3 | 2 |
Na2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 1.5 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 2 | 2 | 2.9 | 0 | 1.5 | 0 | 0 | 0 | 0 | 0 |
WO3 | 4 | 4 | 4 | 4 | 4 | 4 | 3.5 | 3 | 2.5 | 4 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 |
SiO2 | 65.9 | 66.9 | 65.9 | 66.4 | 60.9 | 65.9 | 69.9 | 66 | 65.9 | 65.8 |
B2O3 | 20 | 20 | 20 | 20 | 20 | 15 | 10 | 20 | 20 | 20 |
Al2O3 | 9 | 9 | 9 | 9 | 9 | 9 | 10 | 9 | 9 | 9 |
Li2O | 1 | 0 | 3 | 3 | 6 | 6 | 6 | 3 | 3 | 3 |
Na2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
WO3 | 4 | 4 | 2 | 1.5 | 4 | 4 | 4 | 2 | 2 | 2 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0 | 0.1 | 0.2 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 41 | 42 | 43 | 44 | 45 | 46 | 47 | 48 | 49 | 50 |
SiO2 | 65.6 | 65.8 | 65.9 | 70.1 | 70.1 | 69.85 | 70.35 | 70.1 | 69.9 | 68.1 |
B2O3 | 20 | 20 | 20 | 10.35 | 9.8 | 9.8 | 9.8 | 12.35 | 10.35 | 11.35 |
Al2O3 | 9 | 9 | 9 | 10 | 10 | 10 | 10 | 9 | 10 | 10 |
Li2O | 3 | 3 | 3 | 0 | 8.475 | 8.6 | 8.35 | 7.7 | 8.2 | 8.7 |
Na2O | 0 | 0 | 0 | 8.2 | 1.525 | 1.65 | 1.4 | 0.75 | 1.25 | 1.75 |
K2O | 0 | 0 | 0 | 1.25 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
WO3 | 2 | 2 | 2 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
SnO2 | 0.4 | 0 | 0 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.3 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0.2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 51 | 52 | 53 | 54 | 55 | 56 | 57 | 58 | 59 | 60 | 61 |
SiO2 | 69.85 | 69.85 | 69.85 | 69.85 | 70.25 | 69.85 | 69.35 | 68.85 | 69.1 | 69.75 | 68.75 |
B2O3 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 9.8 | 10.8 |
Al2O3 | 10 | 10 | 10 | 9.75 | 10 | 10 | 9.375 | 10 | 10 | 10 | 10 |
Li2O | 0 | 4 | 8 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 3 |
Na2O | 8.6 | 4.6 | 0.6 | 8.725 | 8.35 | 8.35 | 8.975 | 8.6 | 8.6 | 8.6 | 7.25 |
K2O | 1.65 | 1.65 | 1.65 | 1.775 | 1.4 | 1.4 | 1.4 | 1.65 | 1.65 | 1.65 | 0 |
Cs2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
WO3 | 4 | 4 | 4 | 3.5 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0.1 | 0.5 | 1 | 0 | 0 | 0 | 0.1 |
P2O5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
ZnO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1 | 0 | 0 | 0 |
As2O5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.75 | 0 | 0 |
TABLE 2 |
Compositions of glass ceramics that do not absorb radiation in the UV and NIR |
light ranges. |
Mol % | 62 | 63 | 64 | 65 | 66 | 67 | 68 | 69 | 70 | 71 |
SiO2 | 77.9 | 77.94 | 72.3 | 65.7 | 64.7 | 63.7 | 65.7 | 65.7 | 64.2 | 62.7 |
B2O3 | 20.7 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
Al2O3 | 0 | 0.3 | 3.3 | 6.6 | 6.6 | 0.66 | 5.6 | 4.6 | 8.1 | 9.6 |
Li2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Na2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 0.3 | 0.66 | 3.3 | 6.6 | 6.6 | 6.6 | 7.6 | 8.6 | 6.6 | 6.6 |
WO3 | 1 | 1 | 1 | 1 | 2 | 3 | 1 | 1 | 1 | 1 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 72 | 73 | 74 | 75 | 76 | 77 | 78 | 79 | 80 | 81 |
SiO2 | 62.2 | 60.7 | 62.7 | 60.1 | 63.9 | 63.9 | 63.9 | 66.9 | 67.9 | 65.9 |
B2O3 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 10 | 10 |
Al2O3 | 8.1 | 9.6 | 6.6 | 6.6 | 5 | 9 | 9 | 9 | 10 | 10 |
Li2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 3 | 8 | 10 |
Na2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Cs2O | 6.6 | 6.6 | 6.6 | 6.6 | 7 | 0 | 0 | 0 | 0 | 0 |
WO3 | 3 | 3 | 4 | 6.6 | 4 | 4 | 4 | 1 | 4 | 4 |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 3 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 3 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Mol % | 82 | 83 | 84 | 85 | 86 | 87 | 88 | 89 | 90 | 79 |
SiO2 | 63.9 | 65.8 | 65.9 | 65.75 | 67 | 67 | 70.1 | 69.35 | 70.1 | 70.1 |
B2O3 | 10 | 20 | 20 | 20 | 8.1 | 9.1 | 9.35 | 9.8 | 9.35 | 9.35 |
Al2O3 | 10 | 9 | 9 | 9 | 12.6 | 12.6 | 10 | 10 | 10 | 10 |
Li2O | 12 | 3 | 3 | 3 | 5.1 | 5.1 | 8.242 | 8.35 | 8.7 | 8.7 |
Na2O | 0 | 0 | 0 | 0 | 6.2 | 5.7 | 2.208 | 1.4 | 1.75 | 1.75 |
K2O | 0 | 0 | 0 | 0 | 0.8 | 0.3 | 0 | 0 | 0 | 0 |
Cs2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
WO3 | 4 | 2 | 2 | 2 | 4 | 4 | 4 | 4 | 2.5 | 2.5 |
SnO2 | 0.1 | 0 | 0 | 0 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
La2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Eu2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
MnO2 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
CeO2 | 0 | 0.2 | 0 | 0.2 | 0 | 0 | 0 | 0 | 0 | 0 |
Sb2O3 | 0 | 0 | 0.1 | 0.05 | 0 | 0 | 0 | 0 | 0 | 0 |
MgO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1 | 0 | 0 |
TABLE A |
Crystallization temperatures for crystalline MxWO3 phases. |
Alkali | Crystallization | |
Sample | metal M | Temperature (° C.) |
14 | Li | 593.8 |
15 | Na | 682.2 |
16 | K | 706.3 |
13 | Cs | 714.1 |
TABLE B |
Crystallization temperature ranges for crystalline |
MxWO3 phases in samples having low B2O3 content. |
Crystallization Temperature | ||
Sample | B2O3 (mol %) | Range (° C.) |
37 | 10 | 575-625 |
44 | 10.4 | 500-550 |
46 | 9.8 | 500-575 |
50 | 11.4 | 500-650 |
TABLE C |
Physical properties measured for glass ceramics having compositions selected from Table 1. |
|
2 | 11 | 12 | 13 | 14 | 15 | 16 |
Strain Pt. (° C.) | 495 | 450 | 461 | 505.8 | 512.1 | 497.4 | 497.3 |
Anneal Pt. (° C.) | 557 | 498 | 513 | 566.1 | 563.1 | 552.2 | 553.7 |
Soft Pt. PPV (° C.) | 963.1 | 850.9 | 837.9 | 952.4 | |||
CTE (x10−7/° C.) | 33.5 | 53.2 | 48.6 | 37 | |||
Density (g/cm3) | 2.335 | 2.612 | 2.569 | 2.516 | 2.427 | 2.402 | 2.392 |
Refractive Index | 1.4944 | 1.4997 | |||||
633 nm | |||||||
Refractive Index | 1.4798 | 1.4835 | |||||
1549 nm | |||||||
Properties | 33 | 34 | 35 | 36 | 45 | 46 | 50 |
Strain Pt. (° C.) | 515.1 | 471.2 | 485.2 | 523.9 | 486.8 | 483 | 471.3 |
Anneal Pt. (° C.) | 568.9 | 514.3 | 530.8 | 573.1 | 540.8 | 536.7 | 521.2 |
Soft Pt. PPV | 725.6 | 769.6 | 857.9 | 831.5 | 822.2 | 797.3 | |
(° C.) | |||||||
CTE (x10−7/° C.) | |||||||
Density (g/cm3): | 2.307 | 2.416 | 2.429 | 2.452 | |||
Refractive | |||||||
Index 633 nm | |||||||
Refractive | |||||||
Index 1549 nm | |||||||
Poisson's Ratio | 0.228 | 0.23 | 0.226 | 0.217 | |||
Shear Modulus | 3.47 | 3.48 | 3.65 | 3.95 | |||
Mpsi | |||||||
Young's | 8.53 | 8.56 | 8.96 | 9.61 | |||
Modulus Mpsi | |||||||
Stress Optical | 4.176 | 4.033 | 3.763 | ||||
Coefficient | |||||||
nm/nm/MPa | |||||||
Maximum | >1320 | 1160 | 1175 | 1290 | 1210 | 1210 | 1155 |
Crystallization | |||||||
Temp (° C.) | |||||||
Primary Phase | Unknown | Unknown | Mullite | Mullite | Cassiterite | Cassiterite | Cassiterite |
Comments | Devitrified | Cassiterite | Cassiterite | ||||
to hot end | up to | up to | |||||
1155° C. | 1170° C. | ||||||
Properties | 51 | 52 | 53 | 54 | |
Strain Pt. (° C.) | 489.7 | 466.5 | |||
Anneal Pt. (° C.) | 544.4 | 522.3 | |||
Soft Pt. PPV (° C.) | |||||
CTE (x10−7/° C.) | 64.4 | 57.3 | |||
Density (g/cm3): | |||||
Refractive Index | |||||
633 nm | |||||
Refractive Index | |||||
1549 nm | |||||
Poisson's Ratio | 0.219 | 0.219 | 0.219 | 0.214 | |
Shear Modulus | 0.217 | 3.79 | 3.88 | 3.55 | |
Mpsi | |||||
Young's Modulus | 8.60 | 9.25 | 9.47 | 8.62 | |
Mpsi | |||||
Stress Optical | 3.838 | 3.628 | 3.65 | 3.81 | |
Coefficient | |||||
nm/nm/MPa | |||||
Maximum | |||||
Crystallization | |||||
Temp (° C.) | |||||
Primary Phase | |||||
Comments | |||||
TABLE D |
Heat Treatment temperature and time ranges used |
to produce UV- and NIR- absorbing MxWO3 glass |
ceramics via the melt-quench process. |
Composition | Heat Treatment | Heat Treatment Time |
(Table 1) | Temperature Range (° C.) | Range (hours) |
12 | 520-550 | 20-30 |
13 | 650-725 | 0.5-1.5 |
14 | 575-700 | 0.08-0.5 |
15 | 625-725 | 0.4-2 |
16 | 650-725 | 0.5-2 |
37 | 600-625 | 16-30 |
46 | 525-600 | 0.75-10 |
50 | 525-650 | 0.75-10 |
51 | 525-600 | 0.75-10 |
52 | 525-575 | 1-10 |
53 | 525-575 | 0.5-5 |
61 | 525-650 | 0.2-2 |
TABLE E |
Compositions and refractive indices of rare earth-doped |
aluminosilicate glasses. |
Mol % | A | B | C | D | | F |
MgO | ||||||
0 | 0 | 0 | 9.2 | 8.8 | 8.8 | |
|
0 | 0 | 0 | 9.2 | 8.8 | 8.8 |
|
0 | 6 | 6 | 3.4 | 3.2 | 3.2 |
Al2O3 | 18 | 18 | 18 | 10.7 | 10.2 | 10.2 |
B2O3 | 0 | 0 | 0 | 4.6 | 4.4 | 4.4 |
SiO2 | 70 | 70 | 70 | 62.9 | 59.9 | 59.9 |
Pr2O3 | 12 | 6 | 0 | 0 | 4.8 | 0.0 |
Sm2O3 | 0 | 0 | 6 | 0 | 0 | 4.8 |
RI at | 1.604 | 1.565 | 1.562 | 1.528 | 1.58 | 1.576 |
1550 nm | ||||||
Mol % | E-1 | E-2 | E-3 | E-4 | |
MgO | 8.4 | 8.0 | 7.7 | 7.4 | |
CaO | 8.4 | 8.0 | 7.7 | 7.4 | |
BaO | 3.1 | 3.0 | 2.8 | 2.7 | |
Al2O3 | 9.7 | 9.3 | 8.9 | 8.6 | |
B2O3 | 4.2 | 4.0 | 3.8 | 3.7 | |
SiO2 | 57.2 | 54.7 | 52.4 | 50.3 | |
Pr2O3 | 9.1 | 13.0 | 16.7 | 20.0 | |
Sm2O3 | 0 | 0 | 0 | 0 | |
Mol % | DP | DQ | DR | DT | DU | DW | EC | |
Pr2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
Sm2O3 | 20 | 22 | 18 | 22 | 18 | 22 | 0 | |
Er2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 20 | |
Al2O3 | 16 | 18 | 22 | 22 | 26 | 26 | 18 | |
SiO2 | 64 | 60 | 60 | 56 | 56 | 52 | 62 | |
Mol % | ED | ES | FA | FB | FC | FD | FE | |
Pr2O3 | 0 | 0 | 20 | 20 | 20 | 26 | 28 | |
Sm2O3 | 0 | 26 | 0 | 0 | 0 | 0 | 0 | |
Er2O3 | 22 | 0 | 0 | 0 | 0 | 0 | 0 | |
Al2O3 | 24 | 22 | 20 | 30 | 40 | 20 | 28 | |
|
54 | 52 | 60 | 50 | 40 | 54 | 44 | |
TABLE F |
Compositions of rare earth-doped Zn—Bi-borate glasses. |
Mol % | G | H | I | J | K | L |
ZnO | 26.2 | 26.2 | 28.5 | 21.7 | 21.2 | 25.7 |
Bi2O3 | 4.9 | 4.9 | 19 | 14.6 | 14.3 | 4.8 |
B2O3 | 43.6 | 43.6 | 47.5 | 41.5 | 40.7 | 42.9 |
TeO2 | 5.8 | 5.8 | 0 | 0.0 | 0.0 | 5.7 |
Na2O | 14.1 | 14.1 | 0 | 9.7 | 9.5 | 13.8 |
BaO | 2.4 | 2.4 | 0 | 9.7 | 9.5 | 2.4 |
Pr2O3 | 3 | 0 | 5 | 2.9 | 4.8 | 4.8 |
Sm2O3 | 0 | 3 | 0 | 0 | 0.0 | 0.0 |
RI at | 1.683 | 1.680 | 1.857 | not. | not. | not. |
1550 | measured | measured | measured | |||
nm | ||||||
TABLE G |
Compositions of rare earth-doped aluminophosphate glasses. |
Mol % | M | N | O | P | Q | R | S | |
Sm2O3 | 21 | 17 | 20 | 13.5 | 10 | 13 | 6 | |
Al2O3 | 5 | 10 | 10 | 15 | 20 | 20 | 25 | |
P2O5 | 74 | 73 | 70 | 71.5 | 70 | 67 | 69 | |
Claims (2)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/559,806 US11214511B2 (en) | 2016-06-17 | 2019-09-04 | Transparent, near infrared-shielding glass ceramic |
US17/539,507 US11629091B2 (en) | 2016-06-17 | 2021-12-01 | Transparent, near infrared-shielding glass ceramic |
US18/121,689 US20230322607A1 (en) | 2016-06-17 | 2023-03-15 | Manufacturing tungsten bronze glass ceramic |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662351616P | 2016-06-17 | 2016-06-17 | |
US201662352602P | 2016-06-21 | 2016-06-21 | |
US15/244,534 US20170362119A1 (en) | 2016-06-17 | 2016-08-23 | Transparent, near infrared-shielding glass ceramic |
US16/559,806 US11214511B2 (en) | 2016-06-17 | 2019-09-04 | Transparent, near infrared-shielding glass ceramic |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/244,534 Continuation US20170362119A1 (en) | 2016-06-17 | 2016-08-23 | Transparent, near infrared-shielding glass ceramic |
US15/244,534 Division US20170362119A1 (en) | 2016-06-17 | 2016-08-23 | Transparent, near infrared-shielding glass ceramic |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/539,507 Continuation US11629091B2 (en) | 2016-06-17 | 2021-12-01 | Transparent, near infrared-shielding glass ceramic |
Publications (2)
Publication Number | Publication Date |
---|---|
US20200002220A1 US20200002220A1 (en) | 2020-01-02 |
US11214511B2 true US11214511B2 (en) | 2022-01-04 |
Family
ID=59216082
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/244,534 Abandoned US20170362119A1 (en) | 2016-06-17 | 2016-08-23 | Transparent, near infrared-shielding glass ceramic |
US16/559,806 Active 2036-09-13 US11214511B2 (en) | 2016-06-17 | 2019-09-04 | Transparent, near infrared-shielding glass ceramic |
US17/539,507 Active US11629091B2 (en) | 2016-06-17 | 2021-12-01 | Transparent, near infrared-shielding glass ceramic |
US18/121,689 Pending US20230322607A1 (en) | 2016-06-17 | 2023-03-15 | Manufacturing tungsten bronze glass ceramic |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/244,534 Abandoned US20170362119A1 (en) | 2016-06-17 | 2016-08-23 | Transparent, near infrared-shielding glass ceramic |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/539,507 Active US11629091B2 (en) | 2016-06-17 | 2021-12-01 | Transparent, near infrared-shielding glass ceramic |
US18/121,689 Pending US20230322607A1 (en) | 2016-06-17 | 2023-03-15 | Manufacturing tungsten bronze glass ceramic |
Country Status (12)
Country | Link |
---|---|
US (4) | US20170362119A1 (en) |
EP (2) | EP3442914B1 (en) |
JP (3) | JP7084880B2 (en) |
KR (2) | KR102466477B1 (en) |
CN (2) | CN109311730B (en) |
AU (1) | AU2017285323B2 (en) |
BR (1) | BR112018076280A2 (en) |
CA (1) | CA3028117A1 (en) |
MX (1) | MX2018015928A (en) |
RU (1) | RU2747856C2 (en) |
TW (2) | TWI828563B (en) |
WO (1) | WO2017218859A1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107223116B (en) | 2014-12-11 | 2021-12-07 | 康宁股份有限公司 | X-ray induced coloration in glass or glass-ceramic articles |
US20170362119A1 (en) | 2016-06-17 | 2017-12-21 | Corning Incorporated | Transparent, near infrared-shielding glass ceramic |
US10464840B2 (en) | 2016-10-05 | 2019-11-05 | Corning Incorporated | Near infrared shielding and laser-resistant window |
CN111511696A (en) * | 2017-10-23 | 2020-08-07 | 康宁股份有限公司 | Glass-ceramic and glass |
US10246371B1 (en) * | 2017-12-13 | 2019-04-02 | Corning Incorporated | Articles including glass and/or glass-ceramics and methods of making the same |
US10450220B2 (en) | 2017-12-13 | 2019-10-22 | Corning Incorporated | Glass-ceramics and glasses |
KR20200091448A (en) | 2017-12-04 | 2020-07-30 | 코닝 인코포레이티드 | Glass-ceramic and glass-ceramic articles with UV- and near infrared-blocking characteristics |
US11053159B2 (en) | 2017-12-13 | 2021-07-06 | Corning Incorporated | Polychromatic articles and methods of making the same |
US10829408B2 (en) * | 2017-12-13 | 2020-11-10 | Corning Incorporated | Glass-ceramics and methods of making the same |
CN111479689B (en) * | 2017-12-15 | 2023-07-28 | 康宁股份有限公司 | Laminated glass ceramic article with UV and NIR blocking properties and method of making same |
US11426818B2 (en) | 2018-08-10 | 2022-08-30 | The Research Foundation for the State University | Additive manufacturing processes and additively manufactured products |
EP3880619B1 (en) * | 2018-11-16 | 2023-07-19 | Corning Incorporated | Glass ceramic devices and methods with tunable infrared transmittance |
WO2020106486A1 (en) | 2018-11-21 | 2020-05-28 | Corning Incorporated | Very low total solar transmittance window laminate with visible light tunability |
JP2022520571A (en) * | 2019-02-12 | 2022-03-31 | コーニング インコーポレイテッド | Multicolored glass and glass ceramic articles and their manufacturing methods |
JP2022521892A (en) * | 2019-02-12 | 2022-04-13 | コーニング インコーポレイテッド | Gradient colored articles and their manufacturing methods |
WO2020171967A1 (en) * | 2019-02-20 | 2020-08-27 | Corning Incorporated | Iron- and manganese-doped tungstate and molybdate glass and glass-ceramic articles |
JP6897704B2 (en) * | 2019-03-29 | 2021-07-07 | Tdk株式会社 | Black mark composition and electronic components using it |
WO2020251939A1 (en) * | 2019-06-10 | 2020-12-17 | Baudhuin Thomas J | Apparatus for supercritical water gasification |
JPWO2021256304A1 (en) * | 2020-06-19 | 2021-12-23 | ||
CN114195383B (en) * | 2021-12-27 | 2022-09-09 | 苏州广辰光学科技有限公司 | Preparation process of blue glass for infrared cut-off filter |
WO2023239693A1 (en) * | 2022-06-07 | 2023-12-14 | Corning Incorporated | Methods for forming and tuning local transmittance contrast in glass-ceramic articles via laser bleaching |
Citations (93)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2034994A (en) | 1933-06-26 | 1936-03-24 | Mississippi Glass Co | Heat absorbing glass |
US2952575A (en) | 1958-05-16 | 1960-09-13 | Monsanto Chemicals | Near-infrared spectrum filter media |
US3293052A (en) | 1963-03-14 | 1966-12-20 | Corning Glass Works | Glass article and method of making it |
US3457106A (en) | 1966-12-21 | 1969-07-22 | Ppg Industries Inc | Metal-tungsten bronze films |
US3499775A (en) | 1966-07-01 | 1970-03-10 | Owens Illinois Inc | Ultraviolet-absorbing glass compositions containing cerium and molybdenum oxides |
US3582370A (en) | 1968-11-05 | 1971-06-01 | Corning Glass Works | Glass-ceramic articles |
SU392016A1 (en) | 1971-08-03 | 1973-07-27 | Тбилисский государственный научно исследовательский институт строительных материалов | SEMICONDUCTOR GLASS |
US3779733A (en) | 1970-01-26 | 1973-12-18 | Ppg Industries Inc | Method of manufacturing heat absorbing glass |
US3785834A (en) | 1972-06-09 | 1974-01-15 | Owens Illinois Inc | Glasses,glass-ceramics and process for making same |
US3985534A (en) | 1975-03-19 | 1976-10-12 | Corning Glass Works | Spontaneously-formed fluormica glass-ceramics |
JPS5385813A (en) | 1976-12-30 | 1978-07-28 | Hoya Glass Works Ltd | Spectacle glass having glareeprotection effect |
US4303298A (en) | 1978-04-17 | 1981-12-01 | Hoya Corporation | Near infrared absorption filter for color television cameras |
US4537862A (en) | 1982-06-28 | 1985-08-27 | Owens-Illinois, Inc. | Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating |
US4769347A (en) | 1986-01-06 | 1988-09-06 | Schott Glass Technologies, Inc. | Contrast enhancement filter glass for color CRT displays |
US4792536A (en) | 1987-06-29 | 1988-12-20 | Ppg Industries, Inc. | Transparent infrared absorbing glass and method of making |
US4870539A (en) | 1989-01-17 | 1989-09-26 | International Business Machines Corporation | Doped titanate glass-ceramic for grain boundary barrier layer capacitors |
US5393593A (en) | 1990-10-25 | 1995-02-28 | Ppg Industries, Inc. | Dark gray, infrared absorbing glass composition and coated glass for privacy glazing |
RU2032633C1 (en) | 1990-07-09 | 1995-04-10 | Обнинское научно-производственное предприятие "Технология" | Glass for dark-red glass-crystalline material which is transparent in infrared region of spectra |
US5468694A (en) | 1992-11-21 | 1995-11-21 | Yamamura Glass Co. Ltd. | Composition for producing low temperature co-fired substrate |
TW264422B (en) | 1994-01-20 | 1995-12-01 | Yoshida Kogyo Kk | |
US5565388A (en) | 1993-11-16 | 1996-10-15 | Ppg Industries, Inc. | Bronze glass composition |
JPH09241035A (en) | 1996-03-06 | 1997-09-16 | Central Glass Co Ltd | Crystallized glass |
US5668066A (en) | 1995-07-24 | 1997-09-16 | Hoya Corporation | Near infrared absorption filter glass |
WO1999002461A1 (en) | 1997-07-11 | 1999-01-21 | Ford Motor Company | A blue glass with improved uv and ir absorption |
US6048621A (en) | 1996-09-13 | 2000-04-11 | Pilkington Plc | Coated glass |
US6114264A (en) | 1993-11-16 | 2000-09-05 | Ppg Industries Ohio, Inc. | Gray glass composition |
US6184162B1 (en) | 1998-08-24 | 2001-02-06 | Schott Glas | Glasses and glass-ceramics with high E-moduli |
US6196027B1 (en) | 1996-12-20 | 2001-03-06 | Libbey-Owens-Ford Co. | Method of making glasses containing spectral modifiers |
US6214429B1 (en) | 1996-09-04 | 2001-04-10 | Hoya Corporation | Disc substrates for information recording discs and magnetic discs |
US6274523B1 (en) | 1993-11-16 | 2001-08-14 | Ppg Industris Ohio, Inc. | Gray glass composition |
US20020032113A1 (en) | 1999-06-01 | 2002-03-14 | Kousuke Nakajima | High rigidity glass-ceramic substrate |
US6376399B1 (en) | 2000-01-24 | 2002-04-23 | Corning Incorporated | Tungstate, molybdate, vanadate base glasses |
US20020072461A1 (en) | 1998-06-22 | 2002-06-13 | Yoshinobu Akimoto | Infrared absorbing glass, and its fabrication method |
US20020080474A1 (en) | 1997-02-14 | 2002-06-27 | Nippon Telegraph And Telephone Corporation | Optical fiber splicing structure |
JP2002293571A (en) | 2001-03-30 | 2002-10-09 | Nippon Electric Glass Co Ltd | Glass for illumination |
RU2194807C2 (en) | 1996-11-29 | 2002-12-20 | Йеда Рисерч Энд Дивелопмент Ко., Лтд. | Process generating nonoparticles or filiform nonocrystals, process producing inorganic fuller-like structures of metal chalcogenide, inorganic fuller-like structures of metal chalocogenide, stable suspension of if structures of metal chalcogenide, process of production of thin films from if structures of metal chalcogenide, thin film produced by this process and attachment for scanning microscope |
US6537937B1 (en) | 1999-08-03 | 2003-03-25 | Asahi Glass Company, Limited | Alkali-free glass |
JP2003099913A (en) | 2001-09-27 | 2003-04-04 | Hitachi Ltd | Glass base plate for magnetic disk and magnetic disk using it |
US20030158029A1 (en) | 2001-08-22 | 2003-08-21 | Rolf Clasen | Optical colored glass, it's use, and an optical long-pass cutoff filter |
WO2003097544A1 (en) | 2002-05-16 | 2003-11-27 | Schott Ag | Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
JP2004091308A (en) | 2002-07-11 | 2004-03-25 | Nippon Electric Glass Co Ltd | Glass for lighting |
JP2004206741A (en) | 2002-12-24 | 2004-07-22 | Hitachi Ltd | Glass substrate for magnetic disk, and magnetic disk using the same |
US6899954B2 (en) | 2001-08-22 | 2005-05-31 | Schott Ag | Cadmium-free optical steep edge filters |
US6911254B2 (en) | 2000-11-14 | 2005-06-28 | Solutia, Inc. | Infrared absorbing compositions and laminates |
DE10353756A1 (en) | 2003-11-17 | 2005-06-30 | Bio-Gate Bioinnovative Materials Gmbh | layer material |
US20050181927A1 (en) | 2002-03-29 | 2005-08-18 | Matsushita Electric Industrial Co., Ltd | Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member |
US20060025298A1 (en) | 2004-07-30 | 2006-02-02 | Shepherd Color Company | Durable glass and glass enamel composition for glass coatings |
US20060063009A1 (en) | 2004-09-17 | 2006-03-23 | Takashi Naitou | Glass member |
DE102005051387B3 (en) | 2005-10-27 | 2007-01-25 | Ivoclar Vivadent Ag | Dental glass useful as a filler for dental composites comprises oxides of silicon, aluminum, magnesium, lanthanum, tungsten and zirconium |
US7192897B2 (en) | 2002-07-05 | 2007-03-20 | Hoya Corporation | Near-infrared light-absorbing glass, near-infrared light-absorbing element, near-infrared light-absorbing filter, and method of manufacturing near-infrared light-absorbing formed glass article, and copper-containing glass |
EP1780182A1 (en) | 2005-10-25 | 2007-05-02 | Ohara Inc. | Glass ceramics and a method for manufacturing the same |
US20070158317A1 (en) | 2005-07-06 | 2007-07-12 | Peter Brix | Thin flat glass for display purposes and method of cutting the thin flat glass into display sheets |
JP2007238353A (en) | 2006-03-06 | 2007-09-20 | Sumitomo Metal Mining Co Ltd | Tungsten-containing oxide fine particle, method for manufacturing the same, and infrared light shielding body using the same |
US20070225144A1 (en) | 2004-11-30 | 2007-09-27 | Asahi Glass Co., Ltd. | Crystallized glass spacer for field emission display and method its production |
TW200744975A (en) | 2006-05-16 | 2007-12-16 | Schott Ag | Backlight system with IR absorption properties |
US20080193686A1 (en) | 2005-04-09 | 2008-08-14 | Saint-Gobain Glass France | Multiple Glazing With Improved Selectivity |
US20090215605A1 (en) | 2008-02-26 | 2009-08-27 | Martin Letz | Process of producing a glass-ceramic, the glass-ceramic made therby and its uses |
US7727916B2 (en) | 2001-03-24 | 2010-06-01 | Schott Ag | Alkali-free aluminoborosilicate glass, and uses thereof |
US7820575B2 (en) | 2003-12-26 | 2010-10-26 | Nippon Sheet Glass Company, Limited | Near infrared absorbent green glass composition, and laminated glass using the same |
US7838451B2 (en) | 2003-12-26 | 2010-11-23 | Asahi Glass Company, Limited | Alkali-free glass and liquid crystal display panel |
US7851394B2 (en) | 2005-06-28 | 2010-12-14 | Corning Incorporated | Fining of boroalumino silicate glasses |
US20110028298A1 (en) | 2009-06-04 | 2011-02-03 | Bernd Hoppe | Glass-ceramic containing nanoscale barium titanate and process for the production thereof |
JP2011046599A (en) | 2009-07-31 | 2011-03-10 | Ohara Inc | Crystallized glass and method for manufacturing the same |
EP2360220A1 (en) | 2008-11-13 | 2011-08-24 | Sumitomo Metal Mining Co., Ltd. | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
US8017538B2 (en) | 2004-03-19 | 2011-09-13 | Saint-Gobain Glass France | Dark grey soda-lime silica glass composition which is intended for the production of glazing |
US20110248225A1 (en) | 2009-07-07 | 2011-10-13 | Basf Se | Potassium cesium tungsten bronze particles |
US20120247525A1 (en) | 2011-03-31 | 2012-10-04 | Bruce Gardiner Aitken | Tungsten-titanium-phosphate materials and methods for making and using the same |
US8399547B2 (en) | 2009-12-15 | 2013-03-19 | Bayer Materialscience Ag | Polymer composition with heat-absorbing properties and high stability |
EP2581353A1 (en) | 2010-06-10 | 2013-04-17 | Bridgestone Corporation | Heat-radiation-blocking multi-layered glass |
JP2013242946A (en) | 2012-05-22 | 2013-12-05 | Panasonic Corp | Information recording medium, and method of manufacturing information recording medium |
JP2014094879A (en) | 2012-10-10 | 2014-05-22 | Ohara Inc | Crystallized glass and method for producing the same |
CN103864313A (en) | 2012-12-17 | 2014-06-18 | 财团法人工业技术研究院 | Heat-insulating glass with infrared reflecting multilayer structure and manufacturing method thereof |
US20140232030A1 (en) | 2011-10-14 | 2014-08-21 | Ivoclar Vivadent Ag | Lithium silicate glass ceramic and lithium silicate glass comprising a hexavalent metal oxide |
US20140256865A1 (en) | 2013-03-05 | 2014-09-11 | Honeywell International Inc. | Electric-arc resistant face shield or lens including ir-blocking inorganic nanoparticles |
US20140305929A1 (en) | 2013-04-15 | 2014-10-16 | Schott Ag | Glass ceramic cooking plate with locally increased transmission and method for producing such a glass ceramic cooking plate |
RU2531958C2 (en) | 2012-05-02 | 2014-10-27 | Корпорация "Самсунг Электроникс Ко., Лтд" | Electro-optical laser glass and method for production thereof |
JP2014241035A (en) | 2013-06-11 | 2014-12-25 | キヤノン株式会社 | Server device, image recreation method, and program |
JP2015044921A (en) | 2013-08-27 | 2015-03-12 | 住友金属鉱山株式会社 | Heat ray-shielding dispersion material, coating liquid for forming heat ray-shielding dispersion material, and heat ray-shielding body |
CN104445932A (en) | 2014-12-10 | 2015-03-25 | 中国建材国际工程集团有限公司 | Pink alumina silicate glass |
US20150093554A1 (en) | 2013-10-02 | 2015-04-02 | Eritek, Inc. | Low-emissivity coated glass for improving radio frequency signal transmission |
CN104743882A (en) | 2013-12-27 | 2015-07-01 | 株式会社小原 | Optical object and lens |
CN104944471A (en) | 2015-05-25 | 2015-09-30 | 北京航空航天大学 | Tungsten doped bronze powder having high infrared shielding property and synthesis method of doped tungsten bronze powder |
CN105102389A (en) | 2013-02-28 | 2015-11-25 | 国家科学研究中心 | Nanostructured lenses and vitroceramics that are transparent in visible and infrared ranges |
US20160168023A1 (en) | 2014-12-11 | 2016-06-16 | Corning Incorporated | X-ray induced coloration in glass or glass-ceramic articles |
WO2017129516A1 (en) | 2016-01-27 | 2017-08-03 | Evonik Degussa Gmbh | Process for producing tungsten oxide and tungsten mixed oxides |
JP6206736B2 (en) | 2015-10-28 | 2017-10-04 | パナソニックIpマネジメント株式会社 | Observation system and method using flying object |
US20170362119A1 (en) | 2016-06-17 | 2017-12-21 | Corning Incorporated | Transparent, near infrared-shielding glass ceramic |
CN107601853A (en) | 2017-09-06 | 2018-01-19 | 蚌埠玻璃工业设计研究院 | A kind of photochromic glass with high elastic modulus and preparation method thereof |
WO2019051408A2 (en) | 2017-09-11 | 2019-03-14 | Corning Incorporated | Devices with bleached discrete region and methods of manufacture |
US10246371B1 (en) | 2017-12-13 | 2019-04-02 | Corning Incorporated | Articles including glass and/or glass-ceramics and methods of making the same |
WO2019083937A2 (en) | 2017-10-23 | 2019-05-02 | Corning Incorporated | Glass-ceramics and glasses |
US20190168023A1 (en) | 2017-12-05 | 2019-06-06 | Lumen Catheters, LLC | Method, system, and devices of safe, antimicrobial light-emitting catheters, tubes, and instruments |
US20190177212A1 (en) | 2017-12-13 | 2019-06-13 | Corning Incorporated | Glass-ceramics and glasses |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1104178A (en) * | 1964-06-26 | 1968-02-21 | Corning Glass Works | Tungsten bronze films |
US4009042A (en) | 1976-01-15 | 1977-02-22 | Corning Glass Works | Transparent, infra-red transmitting glass-ceramics |
JP2539214B2 (en) * | 1987-03-31 | 1996-10-02 | 川鉄鉱業株式会社 | Glass ceramics and manufacturing method thereof |
GB9108257D0 (en) | 1991-04-17 | 1991-06-05 | Cookson Group Plc | Glaze compositions |
JP5146897B2 (en) * | 2004-04-05 | 2013-02-20 | 日本電気硝子株式会社 | Glass for lighting |
US7470999B2 (en) * | 2004-09-29 | 2008-12-30 | Nippon Electric Glass Co., Ltd. | Glass for semiconductor encapsulation and outer tube for semiconductor encapsulation, and semiconductor electronic parts |
DE102008025277A1 (en) * | 2008-05-27 | 2009-12-03 | Merck Patent Gmbh | glass composition |
JP5354445B2 (en) * | 2008-06-25 | 2013-11-27 | 日本電気硝子株式会社 | Glass for metal coating and semiconductor sealing material |
WO2010098227A1 (en) * | 2009-02-27 | 2010-09-02 | 国立大学法人長岡技術科学大学 | Optical modulation material and method for producing same |
JP5402184B2 (en) * | 2009-04-13 | 2014-01-29 | 日本電気硝子株式会社 | Glass film and method for producing the same |
CN102421718B (en) * | 2009-07-31 | 2015-08-05 | 株式会社小原 | Glass-ceramic, glass ceramic frit body, glass-ceramic complex body, glass powder plastochondria, pulp-like mixture and photocatalyst |
JP2011241092A (en) * | 2010-04-21 | 2011-12-01 | Ohara Inc | Glass ceramics and method for producing the same |
JP5778488B2 (en) * | 2010-12-22 | 2015-09-16 | 株式会社ブリヂストン | Heat ray shielding glass and multilayer glass using the same |
US9878940B2 (en) | 2014-02-21 | 2018-01-30 | Corning Incorporated | Low crystallinity glass-ceramics |
CN105254181B (en) | 2014-07-18 | 2017-08-11 | 长春理工大学 | A kind of europium doping tungstates transparent glass ceramics and preparation method thereof |
DE102014013528B4 (en) | 2014-09-12 | 2022-06-23 | Schott Ag | Coated glass or glass-ceramic substrate with stable multifunctional surface properties, method for its production and its use |
CN105948513B (en) | 2016-05-16 | 2018-09-21 | 长春理工大学 | Terbium doped transparent glass ceramics of crystalline phase containing calcium molybdate of one kind and preparation method thereof |
CN106396413B (en) | 2016-09-08 | 2018-11-09 | 长春理工大学 | Erbium and ytterbium codoping up-conversion luminescent glass ceramics of crystalline phase containing barium tungstate and preparation method thereof |
KR20200091448A (en) | 2017-12-04 | 2020-07-30 | 코닝 인코포레이티드 | Glass-ceramic and glass-ceramic articles with UV- and near infrared-blocking characteristics |
US10829408B2 (en) | 2017-12-13 | 2020-11-10 | Corning Incorporated | Glass-ceramics and methods of making the same |
US11053159B2 (en) | 2017-12-13 | 2021-07-06 | Corning Incorporated | Polychromatic articles and methods of making the same |
-
2016
- 2016-08-23 US US15/244,534 patent/US20170362119A1/en not_active Abandoned
-
2017
- 2017-06-16 TW TW112110830A patent/TWI828563B/en active
- 2017-06-16 JP JP2018565799A patent/JP7084880B2/en active Active
- 2017-06-16 CN CN201780037677.4A patent/CN109311730B/en active Active
- 2017-06-16 WO PCT/US2017/037809 patent/WO2017218859A1/en active Application Filing
- 2017-06-16 EP EP17733310.1A patent/EP3442914B1/en active Active
- 2017-06-16 MX MX2018015928A patent/MX2018015928A/en unknown
- 2017-06-16 KR KR1020197001381A patent/KR102466477B1/en active IP Right Grant
- 2017-06-16 KR KR1020227038989A patent/KR102664949B1/en active IP Right Grant
- 2017-06-16 CA CA3028117A patent/CA3028117A1/en active Pending
- 2017-06-16 CN CN202210361822.7A patent/CN114685042A/en active Pending
- 2017-06-16 EP EP22151609.9A patent/EP4005988A1/en active Pending
- 2017-06-16 AU AU2017285323A patent/AU2017285323B2/en not_active Ceased
- 2017-06-16 BR BR112018076280-6A patent/BR112018076280A2/en not_active Application Discontinuation
- 2017-06-16 TW TW106120158A patent/TWI806828B/en active
- 2017-06-16 RU RU2019101015A patent/RU2747856C2/en active
-
2019
- 2019-09-04 US US16/559,806 patent/US11214511B2/en active Active
-
2021
- 2021-06-09 JP JP2021096347A patent/JP7473506B2/en active Active
- 2021-12-01 US US17/539,507 patent/US11629091B2/en active Active
-
2023
- 2023-03-15 US US18/121,689 patent/US20230322607A1/en active Pending
- 2023-12-21 JP JP2023215541A patent/JP2024038004A/en active Pending
Patent Citations (124)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2034994A (en) | 1933-06-26 | 1936-03-24 | Mississippi Glass Co | Heat absorbing glass |
US2952575A (en) | 1958-05-16 | 1960-09-13 | Monsanto Chemicals | Near-infrared spectrum filter media |
US3293052A (en) | 1963-03-14 | 1966-12-20 | Corning Glass Works | Glass article and method of making it |
US3499775A (en) | 1966-07-01 | 1970-03-10 | Owens Illinois Inc | Ultraviolet-absorbing glass compositions containing cerium and molybdenum oxides |
US3457106A (en) | 1966-12-21 | 1969-07-22 | Ppg Industries Inc | Metal-tungsten bronze films |
US3582370A (en) | 1968-11-05 | 1971-06-01 | Corning Glass Works | Glass-ceramic articles |
US3779733A (en) | 1970-01-26 | 1973-12-18 | Ppg Industries Inc | Method of manufacturing heat absorbing glass |
SU392016A1 (en) | 1971-08-03 | 1973-07-27 | Тбилисский государственный научно исследовательский институт строительных материалов | SEMICONDUCTOR GLASS |
US3785834A (en) | 1972-06-09 | 1974-01-15 | Owens Illinois Inc | Glasses,glass-ceramics and process for making same |
US3985534A (en) | 1975-03-19 | 1976-10-12 | Corning Glass Works | Spontaneously-formed fluormica glass-ceramics |
JPS5385813A (en) | 1976-12-30 | 1978-07-28 | Hoya Glass Works Ltd | Spectacle glass having glareeprotection effect |
US4303298A (en) | 1978-04-17 | 1981-12-01 | Hoya Corporation | Near infrared absorption filter for color television cameras |
US4537862A (en) | 1982-06-28 | 1985-08-27 | Owens-Illinois, Inc. | Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating |
JPS60235742A (en) | 1984-04-27 | 1985-11-22 | オーエンス‐イリノイ・インコーポレーテツド | Lead-free, cadmium-free and zinc-free glass frit composition |
MX170104B (en) | 1984-04-27 | 1993-08-06 | Owens Illinois Inc | GLASS FRIT COMPOSITIONS FOR GLASSING, ENAMELING AND DECORATING FOODS FOR FOOD SERVICE |
GB2158062A (en) | 1984-04-27 | 1985-11-06 | Owens Illinois Inc | Lead-free and cadmium-free glass frit compositions for glazing enameling and decorating |
FR2563515A1 (en) | 1984-04-27 | 1985-10-31 | Owens Illinois Inc | NON-LEAD, CADMIUM-FREE GLASS SINTER COMPOSITIONS FOR VITRIFICATION, ENAMELLING AND DECORATION |
IT1181882B (en) | 1984-04-27 | 1987-09-30 | Owens Illinois Inc | COMPOSITION OF LEAD-FREE AND CADMIUM-FREE SHOWCASE FOR WINDOWS, GLAZING AND DECORATION |
CA1232619A (en) | 1984-04-27 | 1988-02-09 | Josef Francel | Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating |
DE3514749A1 (en) | 1984-04-27 | 1985-10-31 | Owens-Illinois, Inc., Toledo, Ohio | GLASS FRIT COMPOSITION |
US4769347A (en) | 1986-01-06 | 1988-09-06 | Schott Glass Technologies, Inc. | Contrast enhancement filter glass for color CRT displays |
US4792536A (en) | 1987-06-29 | 1988-12-20 | Ppg Industries, Inc. | Transparent infrared absorbing glass and method of making |
US4870539A (en) | 1989-01-17 | 1989-09-26 | International Business Machines Corporation | Doped titanate glass-ceramic for grain boundary barrier layer capacitors |
RU2032633C1 (en) | 1990-07-09 | 1995-04-10 | Обнинское научно-производственное предприятие "Технология" | Glass for dark-red glass-crystalline material which is transparent in infrared region of spectra |
US5393593A (en) | 1990-10-25 | 1995-02-28 | Ppg Industries, Inc. | Dark gray, infrared absorbing glass composition and coated glass for privacy glazing |
US5468694A (en) | 1992-11-21 | 1995-11-21 | Yamamura Glass Co. Ltd. | Composition for producing low temperature co-fired substrate |
US6114264A (en) | 1993-11-16 | 2000-09-05 | Ppg Industries Ohio, Inc. | Gray glass composition |
US5565388A (en) | 1993-11-16 | 1996-10-15 | Ppg Industries, Inc. | Bronze glass composition |
US6274523B1 (en) | 1993-11-16 | 2001-08-14 | Ppg Industris Ohio, Inc. | Gray glass composition |
TW264422B (en) | 1994-01-20 | 1995-12-01 | Yoshida Kogyo Kk | |
US5566428A (en) | 1994-01-20 | 1996-10-22 | Ykk Corporation | Molded synthetic resin belt connecting device and method of producing the same |
US5668066A (en) | 1995-07-24 | 1997-09-16 | Hoya Corporation | Near infrared absorption filter glass |
JPH09241035A (en) | 1996-03-06 | 1997-09-16 | Central Glass Co Ltd | Crystallized glass |
US6214429B1 (en) | 1996-09-04 | 2001-04-10 | Hoya Corporation | Disc substrates for information recording discs and magnetic discs |
US6048621A (en) | 1996-09-13 | 2000-04-11 | Pilkington Plc | Coated glass |
RU2194807C2 (en) | 1996-11-29 | 2002-12-20 | Йеда Рисерч Энд Дивелопмент Ко., Лтд. | Process generating nonoparticles or filiform nonocrystals, process producing inorganic fuller-like structures of metal chalcogenide, inorganic fuller-like structures of metal chalocogenide, stable suspension of if structures of metal chalcogenide, process of production of thin films from if structures of metal chalcogenide, thin film produced by this process and attachment for scanning microscope |
US6196027B1 (en) | 1996-12-20 | 2001-03-06 | Libbey-Owens-Ford Co. | Method of making glasses containing spectral modifiers |
US20020080474A1 (en) | 1997-02-14 | 2002-06-27 | Nippon Telegraph And Telephone Corporation | Optical fiber splicing structure |
WO1999002461A1 (en) | 1997-07-11 | 1999-01-21 | Ford Motor Company | A blue glass with improved uv and ir absorption |
US20020072461A1 (en) | 1998-06-22 | 2002-06-13 | Yoshinobu Akimoto | Infrared absorbing glass, and its fabrication method |
US6184162B1 (en) | 1998-08-24 | 2001-02-06 | Schott Glas | Glasses and glass-ceramics with high E-moduli |
US20020032113A1 (en) | 1999-06-01 | 2002-03-14 | Kousuke Nakajima | High rigidity glass-ceramic substrate |
US6537937B1 (en) | 1999-08-03 | 2003-03-25 | Asahi Glass Company, Limited | Alkali-free glass |
US6376399B1 (en) | 2000-01-24 | 2002-04-23 | Corning Incorporated | Tungstate, molybdate, vanadate base glasses |
US6911254B2 (en) | 2000-11-14 | 2005-06-28 | Solutia, Inc. | Infrared absorbing compositions and laminates |
US7727916B2 (en) | 2001-03-24 | 2010-06-01 | Schott Ag | Alkali-free aluminoborosilicate glass, and uses thereof |
JP2002293571A (en) | 2001-03-30 | 2002-10-09 | Nippon Electric Glass Co Ltd | Glass for illumination |
US6899954B2 (en) | 2001-08-22 | 2005-05-31 | Schott Ag | Cadmium-free optical steep edge filters |
US20030158029A1 (en) | 2001-08-22 | 2003-08-21 | Rolf Clasen | Optical colored glass, it's use, and an optical long-pass cutoff filter |
JP2003099913A (en) | 2001-09-27 | 2003-04-04 | Hitachi Ltd | Glass base plate for magnetic disk and magnetic disk using it |
CN1286753C (en) | 2002-03-29 | 2006-11-29 | 松下电器产业株式会社 | Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member |
US20050181927A1 (en) | 2002-03-29 | 2005-08-18 | Matsushita Electric Industrial Co., Ltd | Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member |
KR20050025182A (en) | 2002-05-16 | 2005-03-11 | 쇼오트 아게 | Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
WO2003097544A1 (en) | 2002-05-16 | 2003-11-27 | Schott Ag | Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
AU2003214255A1 (en) | 2002-05-16 | 2003-12-02 | Schott Ag | Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
US20050151116A1 (en) | 2002-05-16 | 2005-07-14 | Schott Ag | Uv-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
CN1653007A (en) | 2002-05-16 | 2005-08-10 | 肖特股份有限公司 | UV-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
US7517822B2 (en) | 2002-05-16 | 2009-04-14 | Schott Ag | UV-blocking borosilicate glass, the use of the same, and a fluorescent lamp |
US7192897B2 (en) | 2002-07-05 | 2007-03-20 | Hoya Corporation | Near-infrared light-absorbing glass, near-infrared light-absorbing element, near-infrared light-absorbing filter, and method of manufacturing near-infrared light-absorbing formed glass article, and copper-containing glass |
JP2004091308A (en) | 2002-07-11 | 2004-03-25 | Nippon Electric Glass Co Ltd | Glass for lighting |
JP2004206741A (en) | 2002-12-24 | 2004-07-22 | Hitachi Ltd | Glass substrate for magnetic disk, and magnetic disk using the same |
DE10353756A1 (en) | 2003-11-17 | 2005-06-30 | Bio-Gate Bioinnovative Materials Gmbh | layer material |
US20090035341A1 (en) | 2003-11-17 | 2009-02-05 | Michael Wagener | Coating material |
US7838451B2 (en) | 2003-12-26 | 2010-11-23 | Asahi Glass Company, Limited | Alkali-free glass and liquid crystal display panel |
US7820575B2 (en) | 2003-12-26 | 2010-10-26 | Nippon Sheet Glass Company, Limited | Near infrared absorbent green glass composition, and laminated glass using the same |
US8017538B2 (en) | 2004-03-19 | 2011-09-13 | Saint-Gobain Glass France | Dark grey soda-lime silica glass composition which is intended for the production of glazing |
US20060025298A1 (en) | 2004-07-30 | 2006-02-02 | Shepherd Color Company | Durable glass and glass enamel composition for glass coatings |
US20060063009A1 (en) | 2004-09-17 | 2006-03-23 | Takashi Naitou | Glass member |
US20070225144A1 (en) | 2004-11-30 | 2007-09-27 | Asahi Glass Co., Ltd. | Crystallized glass spacer for field emission display and method its production |
US7365036B2 (en) | 2004-11-30 | 2008-04-29 | Asahi Glass Company, Limited | Crystallized glass spacer for field emission display and method its production |
US20080193686A1 (en) | 2005-04-09 | 2008-08-14 | Saint-Gobain Glass France | Multiple Glazing With Improved Selectivity |
US7851394B2 (en) | 2005-06-28 | 2010-12-14 | Corning Incorporated | Fining of boroalumino silicate glasses |
US20070158317A1 (en) | 2005-07-06 | 2007-07-12 | Peter Brix | Thin flat glass for display purposes and method of cutting the thin flat glass into display sheets |
EP1780182A1 (en) | 2005-10-25 | 2007-05-02 | Ohara Inc. | Glass ceramics and a method for manufacturing the same |
WO2007048670A2 (en) | 2005-10-27 | 2007-05-03 | Ivoclar Vivadent Ag | Dental glass |
US20090113936A1 (en) | 2005-10-27 | 2009-05-07 | Ivoclar Vivadent Ag | Dental Glass |
DE102005051387B3 (en) | 2005-10-27 | 2007-01-25 | Ivoclar Vivadent Ag | Dental glass useful as a filler for dental composites comprises oxides of silicon, aluminum, magnesium, lanthanum, tungsten and zirconium |
EP1940341A2 (en) | 2005-10-27 | 2008-07-09 | Ivoclar Vivadent AG | Dental glass |
US7795164B2 (en) | 2005-10-27 | 2010-09-14 | Ivoclar Vivadent Ag | Dental glass |
JP2007238353A (en) | 2006-03-06 | 2007-09-20 | Sumitomo Metal Mining Co Ltd | Tungsten-containing oxide fine particle, method for manufacturing the same, and infrared light shielding body using the same |
JP5034272B2 (en) | 2006-03-06 | 2012-09-26 | 住友金属鉱山株式会社 | Tungsten-containing oxide fine particles, method for producing the same, and infrared shielding body using the same |
TW200744975A (en) | 2006-05-16 | 2007-12-16 | Schott Ag | Backlight system with IR absorption properties |
US20090109654A1 (en) | 2006-05-16 | 2009-04-30 | Joerg Hinrich Fechner | Backlight system with ir absorption properties |
US20090215605A1 (en) | 2008-02-26 | 2009-08-27 | Martin Letz | Process of producing a glass-ceramic, the glass-ceramic made therby and its uses |
US8141387B2 (en) | 2008-02-26 | 2012-03-27 | Schott Ag | Process of producing a glass-ceramic, the glass-ceramic made therby and its uses |
EP2360220A1 (en) | 2008-11-13 | 2011-08-24 | Sumitomo Metal Mining Co., Ltd. | Infrared blocking particle, method for producing the same, infrared blocking particle dispersion using the same, and infrared blocking base |
US8263509B2 (en) | 2009-06-04 | 2012-09-11 | Schott Ag | Glass-ceramic containing nanoscale barium titanate and process for the production thereof |
US20110028298A1 (en) | 2009-06-04 | 2011-02-03 | Bernd Hoppe | Glass-ceramic containing nanoscale barium titanate and process for the production thereof |
US20110248225A1 (en) | 2009-07-07 | 2011-10-13 | Basf Se | Potassium cesium tungsten bronze particles |
US8268202B2 (en) | 2009-07-07 | 2012-09-18 | Basf Se | Potassium cesium tungsten bronze particles |
JP2011046599A (en) | 2009-07-31 | 2011-03-10 | Ohara Inc | Crystallized glass and method for manufacturing the same |
US8399547B2 (en) | 2009-12-15 | 2013-03-19 | Bayer Materialscience Ag | Polymer composition with heat-absorbing properties and high stability |
EP2581353A1 (en) | 2010-06-10 | 2013-04-17 | Bridgestone Corporation | Heat-radiation-blocking multi-layered glass |
US20120247525A1 (en) | 2011-03-31 | 2012-10-04 | Bruce Gardiner Aitken | Tungsten-titanium-phosphate materials and methods for making and using the same |
US20140232030A1 (en) | 2011-10-14 | 2014-08-21 | Ivoclar Vivadent Ag | Lithium silicate glass ceramic and lithium silicate glass comprising a hexavalent metal oxide |
RU2531958C2 (en) | 2012-05-02 | 2014-10-27 | Корпорация "Самсунг Электроникс Ко., Лтд" | Electro-optical laser glass and method for production thereof |
JP2013242946A (en) | 2012-05-22 | 2013-12-05 | Panasonic Corp | Information recording medium, and method of manufacturing information recording medium |
JP2014094879A (en) | 2012-10-10 | 2014-05-22 | Ohara Inc | Crystallized glass and method for producing the same |
CN103864313A (en) | 2012-12-17 | 2014-06-18 | 财团法人工业技术研究院 | Heat-insulating glass with infrared reflecting multilayer structure and manufacturing method thereof |
CN105102389A (en) | 2013-02-28 | 2015-11-25 | 国家科学研究中心 | Nanostructured lenses and vitroceramics that are transparent in visible and infrared ranges |
US20140256865A1 (en) | 2013-03-05 | 2014-09-11 | Honeywell International Inc. | Electric-arc resistant face shield or lens including ir-blocking inorganic nanoparticles |
EP2805829A1 (en) | 2013-04-15 | 2014-11-26 | Schott AG | Glass ceramic cooking hob with locally increased transmission and method for producing such a glass ceramic cooking hob |
US20140305929A1 (en) | 2013-04-15 | 2014-10-16 | Schott Ag | Glass ceramic cooking plate with locally increased transmission and method for producing such a glass ceramic cooking plate |
JP2014241035A (en) | 2013-06-11 | 2014-12-25 | キヤノン株式会社 | Server device, image recreation method, and program |
JP2015044921A (en) | 2013-08-27 | 2015-03-12 | 住友金属鉱山株式会社 | Heat ray-shielding dispersion material, coating liquid for forming heat ray-shielding dispersion material, and heat ray-shielding body |
US20150093554A1 (en) | 2013-10-02 | 2015-04-02 | Eritek, Inc. | Low-emissivity coated glass for improving radio frequency signal transmission |
CN104743882A (en) | 2013-12-27 | 2015-07-01 | 株式会社小原 | Optical object and lens |
CN104445932A (en) | 2014-12-10 | 2015-03-25 | 中国建材国际工程集团有限公司 | Pink alumina silicate glass |
US20180044224A1 (en) | 2014-12-10 | 2018-02-15 | China Triumph International Engineering Co., Ltd. | Pink aluminosilicate glass |
US20160168023A1 (en) | 2014-12-11 | 2016-06-16 | Corning Incorporated | X-ray induced coloration in glass or glass-ceramic articles |
CN104944471A (en) | 2015-05-25 | 2015-09-30 | 北京航空航天大学 | Tungsten doped bronze powder having high infrared shielding property and synthesis method of doped tungsten bronze powder |
JP6206736B2 (en) | 2015-10-28 | 2017-10-04 | パナソニックIpマネジメント株式会社 | Observation system and method using flying object |
WO2017129516A1 (en) | 2016-01-27 | 2017-08-03 | Evonik Degussa Gmbh | Process for producing tungsten oxide and tungsten mixed oxides |
US20170362119A1 (en) | 2016-06-17 | 2017-12-21 | Corning Incorporated | Transparent, near infrared-shielding glass ceramic |
WO2017218859A1 (en) | 2016-06-17 | 2017-12-21 | Corning Incorporated | Transparent, near infrared-shielding glass ceramic |
EP3442914A1 (en) | 2016-06-17 | 2019-02-20 | Corning Incorporated | Transparent, near infrared-shielding glass ceramic |
CN107601853A (en) | 2017-09-06 | 2018-01-19 | 蚌埠玻璃工业设计研究院 | A kind of photochromic glass with high elastic modulus and preparation method thereof |
WO2019051408A2 (en) | 2017-09-11 | 2019-03-14 | Corning Incorporated | Devices with bleached discrete region and methods of manufacture |
WO2019083937A2 (en) | 2017-10-23 | 2019-05-02 | Corning Incorporated | Glass-ceramics and glasses |
US20190168023A1 (en) | 2017-12-05 | 2019-06-06 | Lumen Catheters, LLC | Method, system, and devices of safe, antimicrobial light-emitting catheters, tubes, and instruments |
US10246371B1 (en) | 2017-12-13 | 2019-04-02 | Corning Incorporated | Articles including glass and/or glass-ceramics and methods of making the same |
US20190177212A1 (en) | 2017-12-13 | 2019-06-13 | Corning Incorporated | Glass-ceramics and glasses |
US10370291B2 (en) | 2017-12-13 | 2019-08-06 | Corning Incorporated | Articles including glass and/or glass-ceramics and methods of making the same |
US10450220B2 (en) | 2017-12-13 | 2019-10-22 | Corning Incorporated | Glass-ceramics and glasses |
Non-Patent Citations (82)
Title |
---|
"How Low-E Glass Works: What is Low-E Glass." PPG Glass Education Center, <www.educationcenter.ppg.com/glasstopics/how_lowe_works.aspx <http://www.educationcenter.ppg.com/glasstopics/how_lowe_works.aspx> > retrieved on Dec. 22, 2015. |
"Window Technologies: Low-E Coatings." Effucient Windows Collaborative, <www.efficientwindows.org/lowe.php> retrieved on Dec. 22, 2015. |
Aitken and Youngman, "Structure-property relationships of WAI and WTi phosphate glasses and their corresponding glass-ceramics" XI BrazGlass, Curitiba, Brazil. Jul. 15, 2017. 30 slides. |
Aitken et al. "Structure-property relationships of WAI and WTi phosphate glass", NCM-13, Halifax, NS, Canada. Jul. 26, 2016. 25 slides. |
Alizadeh et al.; "Effect of Nucleating Agents on the Crystallization Behaviour and Microstructure of SiO2—CaO—MgO (Na2O) Glass-Ceramics"; Journal of the European Ceramic Society; 20 (2000), 775-782. |
Alizadeh et al.; "Study of Bulk Crystallization In MgO—CaO—SiO2—Na2O Glasses in the Prescence of CaF2 and MoO3 Nucleant"; Journal of Materials Science 38 (2003); pp. 1529-1534. |
Aren et al; "Chalcopyrite Culn(Se1-x, Sx)2 Semiconducting Thin Films", Journal of Materials Science Letters; pp. 11761177, 1993. |
Australian Patent Application No. 2017285323, Examination Report No. 1 dated Feb. 11, 2021, 9 pages; Australian Patent Office. |
Automotive Sunroof Market Size Forcast to Reach USD 9.76 Billion by 2022; Published Mar. 24, 2016; Global Markei Insights, Inc. 3 Pages; https://www.gminsights.com/pressrelease/automotive-sunroof-market-report. |
Banlaw; Molybdenum Prices and Molybdenum Price Charts; IPCC; http://www.infomine.com/investment/metal-prices/molybdenum-oxide/. |
Beall and Duke, "Transparent glass ceramics", Journal of Materials Science 4 (1969), pp. 340-352. |
Beecham; "Research Analysis: Infrared Reflective Glazing"; Just Auto; 2 Pages 2013; http://www.just-auto.com/analysis/infrared-reflective-glazing_id140645.aspx. |
Bodnar et al; "Formation and Optical Properties of CulnSe2 Nanocrystals in a Silicate Matrix", Inorganic Materials, vol. 40, No. 8, 2004, p. 797801. Translated From Neorganicheskie Materialy, vol. 40, No. 8, 2004, pp. 915920. |
Chen et al; "Preparation and Near-Infrared Photothermal Conversion Property of Cesium Tungsten Oxide Nanoparticles"; Nanoschale Research Letters, 8; 57; (2013); 8 Pages. |
Chinese Patent Application No. 201780037677.4, Office Action dated Mar. 1, 2021, 7 pages (English Translation Only); Chinese Patent Office. |
Dejneka et al.; "Glass-Ceramics and Methods of Making the Same"; Filed as U.S. Appl. No. 62/598,108, filed Dec. 13, 2017; 38 Pages—Listed as SP17-398PZ. |
Dejneka et al; "Devices With Bleached Discrete Region and Methods of Manufacture"; Filed as U.S. Appl. No. 62/612,848, filed Jan. 2, 2018; 57 Pages—Listed as SP17-257PZ. |
Dejneka et al; "Laminate Glass Ceramic Articles With UV- and NIR-Blocking Characteristics and Methods of Making the Same"; Filed as U.S. Appl. No. 62/599,517, filed Dec. 15, 2017; 50 Pages—Listed as SP17-407PZ. |
Dejneka et al; "Polychromatic Articles and Methods of Making the Same"; Filed as U.S. Appl. No. 52/598,194. filed Dec. 13, 2017; 62 Pages—Listed as SP17-403PZ. |
Dejneka et al; "Tungsten Glass-Ceramics With a Sharp Cutoff Wavelength"; Filed as U.S. Appl. No. 62/575,763, filed Oct. 23, 2017; 43 Pages—Listed as SP17-309PZ. |
Dejneka, "The luminescence and structure of novel transparent oxyfluoride glass-ceramics", Journal of Non-Crystalline Solids 239 (1998) pp. 149-155. |
Dejneka, "Transparent oxyflouride glass ceramics" MRS Bulliten, Nov. 1998, pp. 57-62. |
Dutta et al. "In-situ characterization of conductive W-Ti Phosphate Glass-Ceramics" GOMD Conference, 2016, Madison, WI. 17 slides. |
Ecoflo; "What Are the RCRA 9 Metals?"; Downloaded Jan. 10, 2019; 4 Pages; https://www.ecoflo.com/2014/12/19/what-are-the-rcra-8-metals/. |
Efficient Window Collaborative; Window Technologies: (technologies.php) Low-E Coatings; Copyright 2000-2018; 8 Pages. |
El-Sayed et al; "Some Properties of Sodium Tungsten Bronzes as a Function of Sodium Concentration"; Indian Journal of Chemical Technology; vol. 12, May 2005; pp. 304-308. |
European Commission; "12 Lead Cadmium in Optical Glass"; (2011); 7 Pages; 2. http://rohs.exemptions.beko.info/fileadmin/user_upload/Rohs_V/Request_12/12_Lead_Cadmium_in_Optical_Glass_2011-08-09.pdf. |
F. Shi, J. Liu, X. Dong, Q. Xu, J. Luo, H. Ma, "Hydrothermal Synthesis of CsxWO3 and the Effects of N2 annealing on its Microstructure and Heat Shielding Properties", J. Mater. Sci. Technol., 30 [4], 342 (2014). |
Gabuni et al; "A Study of the Process of Doping High-Aluminium-Ferruginous Glasses With Small Additions of Some Oxides"; Thesis. Leningrad, 1963; 4 Pages. |
Gabuniya et al; "Study of the Process of Alloying High-Content Aluminum-Iron Glass With Small Admixtures of Various Oxides"; Ministry for the Construction Materials Industry of the Georgian SSR Scientific and Technical Association "Gruzniistrom" Tbilisi Scientific Research Institute for Construction Material; Issue IX; (1975), 7 Pages. |
GL-20, PPG Industires, Inc; http://www.pgwglass.com/products/Pages/OEMgVistaGrayGL-20.aspx. |
Guo et al.; "Highly Efficient Ablation of Metastatic Breast Cancer Using Ammonium-Tungsten-Bronze Nanocube as a Novel 1064 Nm-Laser-Driven Photothermal Agent" Biomaterials; 52 (2015) pp. 407-416. |
H. Tawarayama, F. Utsuno, H. Inoue, H. Hosono, and H. Kawazoe, "Coloration and Decoloration of Tungsten Phosphate Glasses by Heat Treatments at the Temperature Far below Tg", Chem. Mater. 18, 2810 (2006). |
http://cars.axlegeeks.com/d/x/Panorama-Sunroof. |
http://www.wsj.com/articles/SB10001424127887324024004578173271481039256. |
Hussain; "Optical and Electrochromic Properties of Annealed Lithium-Molybdenum-Bronze Thin Films"; Journal of Electronic Materials; vol. 31, No. 6, (2002) pp. 615-630. |
International Search Report and Written Opinion of the International Searching Authority; PCT/US2017/037809; Mailed Oct. 18, 2017; 16 Pages; European Patent Office. |
International Searching Authority Invitation To Pay Additional Fees PCT/US2017/037809 Dated Aug. 25, 2017. |
J. Y. Kim, H. J. Yoon, E. K. Kim, S. Y. Jeong, G. J. Shin, S. Lee, and K. H. Choi, "Near Infrared Cut-off Characteristics of various Perovskite-based Composite Films", IPCBEE, 43, 9 (2012). |
Japanese Patent Application No. 2018-565799, Office Action dated Apr. 8, 2021, 6 pages (3 pages of English Translation and 3 pages of Original Document); Japanese Patent Office. |
K. Adachi, Y. Ota, H. Tanaka, M. Okada, N. Oshimura, and A. Tofuku, "Chromatic instabilities in cesium-doped tungsten bronze nanoparticles", J. Appl. Phys., 115 194304 (2013). |
K. Moon, J. J. Cho, Y. B. Lee, P. J. Yoo, C. W. Bark, and J. Park, "Near Infrared Shielding Properties of Quarternary Tungsten bronze Nanoparticles Na0.11Cs0.22WO3", Bull. Korean Chem. Soc. 34 [3], 731 (2013). |
K.A. Kaliyev, "What are Tungsten Bronzes", EIR vol. 20, No. 17, Apr. 30, 1993. |
Kamel et al; "Effect of The Ce Content on a Nuclear Waste Glassy Matrix in the System SiO2—Al2O3—CaO—MgO—ZrO2—TiO2, Synthesized at a Low Melting Temperature"; Journal of Materials Science and Engineering, A; 3 (4) (2013) pp. 209-223. |
Kawamoto et al; "Effects of Crystallization on Thermal Properties and Chemical Durability of the Glasses Containing Simulated High Level Radioactive Wastes"; Bull. Governm.Ind.Res.Inst.Osaka, 1978, vol. 29, No. 2, p. 168. |
Knoche et al; "Melt Densities for Leucogranites and Granitic Pegmatites: Partial Molar vols. for SiO2, Al2O3, Na2O, K2O, Li2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO, B2O3, P2O5, F2O-1, TiO2, Nb2O5, Ta2O5, and WO3"; Geochimica et Cosmochimica Acta, vol. 59, No. 22 (1995) pp. 4645-4652. |
L. Brickwedel, J. E. Shelby, "Formation and properties of sodium tungsten borate glasses", Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, 5, 598 (2006). |
Lee et al.; "A Study On Toughened Glass Used for Vehicles and Its Testing Methods"; 8 Pages; Date Unknown; http://www-esv.nhtsa.dot.gov/Proceedings/24/files/24ESV-000152.PDF. |
Low-E Glass; Blending Natural Views With Solar Efficiency; http://www.ppgideascapes.com/Glass/Products/Low-E-Glass.aspx. |
M. Green and Z. Hussain, "Optical properties of dilute hydrogen tungsten bronze thin films", J. Appl. Phys. 74, 3451 (1993). |
M. Green and Z. Hussain, "Optical properties of lithium tungsten bronze thin films", J. Appl. Phys. 81, 3592 (1997). |
M. Von Dirke, S. Mller, K. Brner, and H. Rager, "Cluster formation of WO3 in Li2B4O7 glasses", J. Non Crys. Sol., 124, 265 (1990). |
Matthew J. Dejneka; Transparent Oxyfluoride Glass Ceramics; MRS Bulletin; Nov. 1998; pp. 57-62; https:/www.cambridge.org/core. |
Miyazaki, "Fabrication of UV-opaque and visible transparent composite film", Solar Energy Materials & Solar Cells 90 (2006), pp. 2640-2646. |
Moore et al. "Microstructural evolution of conductive WTi phosphate glass-ceramics" GOMD, Madison, WI. May 26, 2016. 18 slides. |
Motortrend; From Coupes to Wagons, Some Cars Less Than $50,000 Have an Extra-Large Sunroof; 33 Pages; Date Unknown; http://www.motortrend.com/news/vehicles-offering-panoramic-sunroofs-for-less-than-50000/. |
Official Newsletter of the Committee on Inventions and Discoveries Under the Council of Lministers of the USSR 50th Publication Year; Discoveries, Inventions; Industrial Prototypes; Trade Marks; Jul. 27, 1973; 3 Pages. |
P. G. Dickens and M. S. Whittingham, "The Tungsten Bronzes and Related Compounds", J. Amer. Chem. Soc., 81,5556 (1981). |
Paradis et al. "Doped vanadium dioxide with enhanced infrared modulation", Sep. 2007, Defense and Research Development Canada. |
Pinet et al; "Redox Effect of Waste Containment Glass Properties: Case of a Borosilicate Glass Containing 16 WT% MoO3"; Proc. XIX Int. Congr. Glass, Eidinburgh, Jul. 1-6, 2001, Glass Technology, 2002, 43C pp. 158-161. |
Poirier et al; "Redox Behavior of Molybdenum and Tungsten in Phosphate Glasses" ; J. Phys. Chem B.; 112; (2008); pp. 4481-4487. |
Pricing; Metal Bulletin Historical Tungsten Pricing (Annual Mean Averages); 2 Pages; https://knoema.com/UNCTADFMCP2015Feb/free-market-commodity-prices-July-2016?tsld=1001760. |
Profita et al; "What You Need To Know About Heavy Metals Pollution in Portland"; OPB; 13 Pages (2016) http://www.opb.org/news/article/what-you-need-to-know-about-heavy-metals-pollution-in-portland/. |
Rouhani, "Photochromism of Molybdenum Oxude", National University of Singapore, PhD Thesis, NUS Graduate School for Integrative Sciences and Enginnering, 2013; 139 Pages. |
Russian Patent Application No. 2019101015, Decision to Grant dated Mar. 16, 2021, 13 pages (6 pages of English Translation and 7 pages of Original Document); Russian Patent Office. |
S. Sakka, "Formation of Tungsten Bronze and Other Electrically Conducting Crystals by Crystallization of Glasses Containing Alkali and Tungsten Oxide", Bull. Inst Chem. Res., Kyoto Univ., 48 [4-5], 185 (1970). |
Saflex® SG Solar Absorbing PVB, Advanced Interlayer Technology for Laminated Glass; 2015; 2 Pages; https://www.saflex.com/pdf/en/AI-Arch-009a_Saflex_SG_Solar_A4.pdf. |
Saint-Gobain Thermocontrol Venus; Copyright 2013; 1 Page; http://saint-gobain-autover.com/thermocontrol-venus-for-auto-glass. |
Solar Energy Spectrum; 1 Page; Date Unknown; http://educationcenter.ppg.com/images/glasstopics/LOW-E%20COATING%201.jpg. |
Solar Energy Spectrum; 1 Page; Date Unknown; https://www.saflex.com/pdf/en/sseriesproductbrochure.pdf. |
Song et al; "Hydrophilic Molybdenum Oxide Nanomaterials With Controlled Morphology and Strong Plasmonic Absorption OFR Photothermal Ablation of Cancer Cells"; ACS Appl. Mater. Interfaces, 6; (2014); pp. 3915-3922. |
Spectaris; "Exemption Renewal Reqeust Form"; 29 Pages; Date Unknown; 1. http://rohs.exemptions.oeko.info/fileadmin/user_upload/RoHS_Pack_7/Exemption_13b/Spectaris_Exemption_Renewal_Request_13b_Final.pdr. |
Status of US. federal trademark registration for the "GL-20" word mark, filed on Aug. 28, 1996, abandoned as of Aug. 30, 1998. |
Sunroof; Wikipedia; Last Updated Nov. 9, 2017; 2 Pages; https://en.wikipedia.org/wiki/Sunroof. |
Taiwanese Patent Application No. 106120158, Office Action dated Mar. 31, 2021, 5 pages (English Translation Only); Taiwanese Patent Office. |
Tanaka et al; "Phase Separation of Borosilcate Glass With Molybdenum Oxide Addition and Pore Structure of Porous Glass"; J. Ceram. Assoc. Japn, vol. 93 [1083], 700-707 (1985). |
Tetchi Fabrice Achille et al. "contribution to light transmittance modelling in starch media" African Journal of Biotechnology; Mar. 5, 2007; pp. 569-575; 6(5. |
Vitro "Radio and Microwave Frequency Attenuation in Glass", Vitro Glass Technical Document TD-151,Vitro Architectural Glass, Oct. 4, 2016, 5 pages. Found at https://www.vitroglazings.com/media/1I1k3zcc/vitro-td-151.pdf .(Year: 2016). * |
Wakeham et al.; "Investigation of Tin-Based Alternatives for Cadmium in Optoelectronic Thin-Film Materials", Appl. Optics, 47, [13], May (2008). |
Wen et al; "Water Resistance of a New Nonlead Phosphate Sealing Glass"; Phys. Chem. Glasses, 43, (3) (2002) pp. 158-160. |
X. Zeng, Y. Zhou, S. Ji, H. Luo, H. Yao, X. Huang, and P. Jin, "The preparation of a high performance near-infrared shielding CsxW03/SiO2 composite resin coating and research on its optical stability under ultraviolet illumination" , J. Mater. Chem. C, 3, 8050 (2015). |
Zhou et al. "CsxWO3 nanoparticle-based organic polymer transparent foils: low haze, high near-infrared sheilding ability and excellent photocromic stability" Journal of Materials Chemistry 5, C, 2017, pp. 6251-6258. |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11629091B2 (en) | Transparent, near infrared-shielding glass ceramic | |
TWI811252B (en) | Glass-ceramics and glasses | |
US11643359B2 (en) | Glass-ceramics and glasses | |
JP7449860B2 (en) | Glass ceramic and its manufacturing method | |
KR20240068776A (en) | Transparent, near infrared-shielding glass ceramic | |
GB2433498A (en) | Glass composition for poling and non-linear optical glass material, and non-linear optical element |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: APPLICATION DISPATCHED FROM PREEXAM, NOT YET DOCKETED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: EX PARTE QUAYLE ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO EX PARTE QUAYLE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT RECEIVED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
CC | Certificate of correction |